JPH0267232A - Novel p-terphenyl derivative and liquid crystal composition - Google Patents
Novel p-terphenyl derivative and liquid crystal compositionInfo
- Publication number
- JPH0267232A JPH0267232A JP63216294A JP21629488A JPH0267232A JP H0267232 A JPH0267232 A JP H0267232A JP 63216294 A JP63216294 A JP 63216294A JP 21629488 A JP21629488 A JP 21629488A JP H0267232 A JPH0267232 A JP H0267232A
- Authority
- JP
- Japan
- Prior art keywords
- terphenyl
- fluoro
- liquid crystal
- oxy
- brombiphenyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 23
- 239000000203 mixture Substances 0.000 title claims description 47
- XJKSTNDFUHDPQJ-UHFFFAOYSA-N 1,4-diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 XJKSTNDFUHDPQJ-UHFFFAOYSA-N 0.000 title claims description 14
- 239000000126 substance Substances 0.000 claims abstract description 37
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 13
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims 4
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 20
- 238000006880 cross-coupling reaction Methods 0.000 abstract description 4
- 230000004044 response Effects 0.000 abstract description 4
- 230000021736 acetylation Effects 0.000 abstract description 3
- 238000006640 acetylation reaction Methods 0.000 abstract description 3
- 238000006266 etherification reaction Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 238000006220 Baeyer-Villiger oxidation reaction Methods 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 102
- 239000000243 solution Substances 0.000 description 69
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 63
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 48
- 239000000047 product Substances 0.000 description 46
- 238000006243 chemical reaction Methods 0.000 description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- 239000002994 raw material Substances 0.000 description 32
- 238000003756 stirring Methods 0.000 description 31
- 238000004128 high performance liquid chromatography Methods 0.000 description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 239000002904 solvent Substances 0.000 description 26
- 238000004458 analytical method Methods 0.000 description 24
- 150000001793 charged compounds Chemical class 0.000 description 24
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 21
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 20
- 229910052938 sodium sulfate Inorganic materials 0.000 description 20
- 235000011152 sodium sulphate Nutrition 0.000 description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 238000010992 reflux Methods 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- UVBFFPZGOOKWNR-UHFFFAOYSA-N 1-bromo-4-octoxybenzene Chemical compound CCCCCCCCOC1=CC=C(Br)C=C1 UVBFFPZGOOKWNR-UHFFFAOYSA-N 0.000 description 11
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 11
- 239000007818 Grignard reagent Substances 0.000 description 11
- 150000004795 grignard reagents Chemical class 0.000 description 11
- 238000010898 silica gel chromatography Methods 0.000 description 11
- -1 4-methylhexyl Chemical group 0.000 description 10
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 10
- 239000003480 eluent Substances 0.000 description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 description 10
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 10
- SPOMGWMYLTYYMO-LBPRGKRZSA-N 4-bromo-2-fluoro-1-[4-[(2s)-2-methylbutoxy]phenyl]benzene Chemical group C1=CC(OC[C@@H](C)CC)=CC=C1C1=CC=C(Br)C=C1F SPOMGWMYLTYYMO-LBPRGKRZSA-N 0.000 description 9
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 9
- 239000010446 mirabilite Substances 0.000 description 9
- XKVLZBNEPALHIO-YFKPBYRVSA-N (2s)-1-bromo-2-methylbutane Chemical compound CC[C@H](C)CBr XKVLZBNEPALHIO-YFKPBYRVSA-N 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 8
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 description 8
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 239000004990 Smectic liquid crystal Substances 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- 239000012267 brine Substances 0.000 description 6
- 230000008034 disappearance Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 239000005457 ice water Substances 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- QIXNVYCYRYRCAK-ZETCQYMHSA-N (4s)-1-bromo-4-methylhexane Chemical compound CC[C@H](C)CCCBr QIXNVYCYRYRCAK-ZETCQYMHSA-N 0.000 description 4
- IOHLFWGBBXATQA-UHFFFAOYSA-N 4-bromo-2-fluoro-1-octoxybenzene Chemical compound CCCCCCCCOC1=CC=C(Br)C=C1F IOHLFWGBBXATQA-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 4
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 4
- 239000003518 caustics Substances 0.000 description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 101150032584 oxy-4 gene Proteins 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- JZJSOSKVBYYDHQ-UHFFFAOYSA-N 1-bromo-4-(4-octoxyphenyl)benzene Chemical group C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(Br)C=C1 JZJSOSKVBYYDHQ-UHFFFAOYSA-N 0.000 description 3
- SWTGVSCSSDYINB-UHFFFAOYSA-N 1-bromo-4-decylbenzene Chemical compound CCCCCCCCCCC1=CC=C(Br)C=C1 SWTGVSCSSDYINB-UHFFFAOYSA-N 0.000 description 3
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 description 3
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 description 3
- JTOLKXNUYODIJI-UHFFFAOYSA-N 4-bromo-2-fluoro-1-(4-octylphenyl)benzene Chemical group C1=CC(CCCCCCCC)=CC=C1C1=CC=C(Br)C=C1F JTOLKXNUYODIJI-UHFFFAOYSA-N 0.000 description 3
- HTRNHWBOBYFTQF-UHFFFAOYSA-N 4-bromo-2-fluoro-1-phenylbenzene Chemical group FC1=CC(Br)=CC=C1C1=CC=CC=C1 HTRNHWBOBYFTQF-UHFFFAOYSA-N 0.000 description 3
- UWDMKTDPDJCJOP-UHFFFAOYSA-N 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-ium-4-carboxylate Chemical compound CC1(C)CC(O)(C(O)=O)CC(C)(C)N1 UWDMKTDPDJCJOP-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 3
- 239000012346 acetyl chloride Substances 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229930184652 p-Terphenyl Natural products 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- DIVCBWJKVSFZKJ-LURJTMIESA-N (4s)-4-methylhexanoic acid Chemical compound CC[C@H](C)CCC(O)=O DIVCBWJKVSFZKJ-LURJTMIESA-N 0.000 description 2
- FZFXOEUVGCHONA-UHFFFAOYSA-N 1-[4-(4-bromo-2-fluorophenyl)phenyl]ethanone Chemical group C1=CC(C(=O)C)=CC=C1C1=CC=C(Br)C=C1F FZFXOEUVGCHONA-UHFFFAOYSA-N 0.000 description 2
- LPLQENSHGFQCRT-UHFFFAOYSA-N 1-[4-(4-phenylphenyl)phenyl]decan-1-one Chemical group C1=CC(C(=O)CCCCCCCCC)=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 LPLQENSHGFQCRT-UHFFFAOYSA-N 0.000 description 2
- KBAGYDCKVAKSFS-UHFFFAOYSA-N 1-bromo-4-decoxybenzene Chemical compound CCCCCCCCCCOC1=CC=C(Br)C=C1 KBAGYDCKVAKSFS-UHFFFAOYSA-N 0.000 description 2
- GKLMJONYGGTHHM-UHFFFAOYSA-N 1-bromo-4-hexoxybenzene Chemical compound CCCCCCOC1=CC=C(Br)C=C1 GKLMJONYGGTHHM-UHFFFAOYSA-N 0.000 description 2
- SGCJPYYTVBHQGE-UHFFFAOYSA-N 1-bromo-4-pentylbenzene Chemical compound CCCCCC1=CC=C(Br)C=C1 SGCJPYYTVBHQGE-UHFFFAOYSA-N 0.000 description 2
- PKJBWOWQJHHAHG-UHFFFAOYSA-N 1-bromo-4-phenylbenzene Chemical group C1=CC(Br)=CC=C1C1=CC=CC=C1 PKJBWOWQJHHAHG-UHFFFAOYSA-N 0.000 description 2
- FYHRDVRDAHXOEJ-UHFFFAOYSA-N 1-decyl-4-(4-phenylphenyl)benzene Chemical group C1=CC(CCCCCCCCCC)=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 FYHRDVRDAHXOEJ-UHFFFAOYSA-N 0.000 description 2
- HFHFGHLXUCOHLN-UHFFFAOYSA-N 2-fluorophenol Chemical compound OC1=CC=CC=C1F HFHFGHLXUCOHLN-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- ARUBXNBYMCVENE-UHFFFAOYSA-N 4-(4-bromophenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=C(Br)C=C1 ARUBXNBYMCVENE-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- ZFYJFIXRMANMPW-UHFFFAOYSA-N 4-bromo-1-(4-decoxyphenyl)-2-fluorobenzene Chemical group C1=CC(OCCCCCCCCCC)=CC=C1C1=CC=C(Br)C=C1F ZFYJFIXRMANMPW-UHFFFAOYSA-N 0.000 description 2
- GNHQJBAQBHWKSP-UHFFFAOYSA-N 4-bromo-2-fluoro-1-(4-octoxyphenyl)benzene Chemical group C1=CC(OCCCCCCCC)=CC=C1C1=CC=C(Br)C=C1F GNHQJBAQBHWKSP-UHFFFAOYSA-N 0.000 description 2
- VWWPCKSNGJFQCW-SNVBAGLBSA-N 4-bromo-2-fluoro-1-[(2r)-heptan-2-yl]oxybenzene Chemical compound CCCCC[C@@H](C)OC1=CC=C(Br)C=C1F VWWPCKSNGJFQCW-SNVBAGLBSA-N 0.000 description 2
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 2
- DIVCBWJKVSFZKJ-UHFFFAOYSA-N 4-methylhexanoic acid Natural products CCC(C)CCC(O)=O DIVCBWJKVSFZKJ-UHFFFAOYSA-N 0.000 description 2
- DGFTWBUZRHAHTH-UHFFFAOYSA-N 4-pentylaniline Chemical compound CCCCCC1=CC=C(N)C=C1 DGFTWBUZRHAHTH-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- YNJWKWKTYUQIEO-ZDUSSCGKSA-N [(2s)-heptan-2-yl] 4-methylbenzenesulfonate Chemical compound CCCCC[C@H](C)OS(=O)(=O)C1=CC=C(C)C=C1 YNJWKWKTYUQIEO-ZDUSSCGKSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000005661 deetherification reaction Methods 0.000 description 2
- 239000012954 diazonium Substances 0.000 description 2
- 150000001989 diazonium salts Chemical class 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- CRWJEUDFKNYSBX-UHFFFAOYSA-N sodium;hypobromite Chemical compound [Na+].Br[O-] CRWJEUDFKNYSBX-UHFFFAOYSA-N 0.000 description 2
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- YNPVNLWKVZZBTM-ZETCQYMHSA-N (4s)-4-methylhexan-1-ol Chemical compound CC[C@H](C)CCCO YNPVNLWKVZZBTM-ZETCQYMHSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VRSVGXQCVFHBOU-UHFFFAOYSA-N 1-[4-(4-bromo-2-fluorophenyl)phenyl]octan-1-one Chemical group C1=CC(C(=O)CCCCCCC)=CC=C1C1=CC=C(Br)C=C1F VRSVGXQCVFHBOU-UHFFFAOYSA-N 0.000 description 1
- YSVZLEKZSJXUFU-UHFFFAOYSA-N 1-[4-[2-fluoro-4-(4-pentylphenyl)phenyl]phenyl]ethanone Chemical group C1=CC(CCCCC)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(C)=O)C(F)=C1 YSVZLEKZSJXUFU-UHFFFAOYSA-N 0.000 description 1
- NFIPMKGEDLEJPD-NSHDSACASA-N 1-bromo-4-[(4s)-4-methylhexoxy]benzene Chemical compound CC[C@H](C)CCCOC1=CC=C(Br)C=C1 NFIPMKGEDLEJPD-NSHDSACASA-N 0.000 description 1
- OYMQBFRXOAOHKA-GDLZYMKVSA-N 1-decyl-4-[4-[4-[(2r)-heptan-2-yl]oxyphenyl]phenyl]benzene Chemical group C1=CC(CCCCCCCCCC)=CC=C1C1=CC=C(C=2C=CC(O[C@H](C)CCCCC)=CC=2)C=C1 OYMQBFRXOAOHKA-GDLZYMKVSA-N 0.000 description 1
- FTYZRYBIIAOURZ-UHFFFAOYSA-N 1-fluoro-2-(4-phenylphenyl)benzene Chemical group FC1=CC=CC=C1C1=CC=C(C=2C=CC=CC=2)C=C1 FTYZRYBIIAOURZ-UHFFFAOYSA-N 0.000 description 1
- UXILLNWRPSFJBA-LLVKDONJSA-N 1-fluoro-2-[(2r)-heptan-2-yl]oxybenzene Chemical compound CCCCC[C@@H](C)OC1=CC=CC=C1F UXILLNWRPSFJBA-LLVKDONJSA-N 0.000 description 1
- TXGOVZRORHWLTQ-UHFFFAOYSA-N 2-(4-bromo-2-fluorophenyl)phenol Chemical group OC1=CC=CC=C1C1=CC=C(Br)C=C1F TXGOVZRORHWLTQ-UHFFFAOYSA-N 0.000 description 1
- OSTDERLNPJJDOI-UHFFFAOYSA-N 2-fluoro-4-(3-fluoro-4-octoxyphenyl)-1-(4-octylphenyl)benzene Chemical group C1=C(F)C(OCCCCCCCC)=CC=C1C1=CC=C(C=2C=CC(CCCCCCCC)=CC=2)C(F)=C1 OSTDERLNPJJDOI-UHFFFAOYSA-N 0.000 description 1
- NOLISAJMAZDTMI-UHFFFAOYSA-N 2-fluoro-4-(4-pentylphenyl)-1-phenylbenzene Chemical group C1=CC(CCCCC)=CC=C1C1=CC=C(C=2C=CC=CC=2)C(F)=C1 NOLISAJMAZDTMI-UHFFFAOYSA-N 0.000 description 1
- FFCWWONROIDGGP-SANMLTNESA-N 2-fluoro-4-[4-[(4s)-4-methylhexoxy]phenyl]-1-(4-octylphenyl)benzene Chemical group C1=CC(CCCCCCCC)=CC=C1C1=CC=C(C=2C=CC(OCCC[C@@H](C)CC)=CC=2)C=C1F FFCWWONROIDGGP-SANMLTNESA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- WOIQLQNFGBYUQN-UHFFFAOYSA-N 4-(4-bromo-2-fluorophenyl)phenol Chemical group C1=CC(O)=CC=C1C1=CC=C(Br)C=C1F WOIQLQNFGBYUQN-UHFFFAOYSA-N 0.000 description 1
- OGWXHTBKWKWANR-UHFFFAOYSA-N 4-bromo-2-fluoro-1-(4-hexoxyphenyl)benzene Chemical group C1=CC(OCCCCCC)=CC=C1C1=CC=C(Br)C=C1F OGWXHTBKWKWANR-UHFFFAOYSA-N 0.000 description 1
- QPGXLJCZANYUSH-AWEZNQCLSA-N 4-bromo-2-fluoro-1-[4-[(2s)-heptan-2-yl]oxyphenyl]benzene Chemical group C1=CC(O[C@@H](C)CCCCC)=CC=C1C1=CC=C(Br)C=C1F QPGXLJCZANYUSH-AWEZNQCLSA-N 0.000 description 1
- QGXAKXCLPXKZQY-AWEZNQCLSA-N 4-bromo-2-fluoro-1-[4-[(4s)-4-methylhexoxy]phenyl]benzene Chemical group C1=CC(OCCC[C@@H](C)CC)=CC=C1C1=CC=C(Br)C=C1F QGXAKXCLPXKZQY-AWEZNQCLSA-N 0.000 description 1
- WGENWPANMZLPIH-UHFFFAOYSA-N 4-decylaniline Chemical compound CCCCCCCCCCC1=CC=C(N)C=C1 WGENWPANMZLPIH-UHFFFAOYSA-N 0.000 description 1
- YNPVNLWKVZZBTM-UHFFFAOYSA-N 4-methylhexan-1-ol Chemical compound CCC(C)CCCO YNPVNLWKVZZBTM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- YNJWKWKTYUQIEO-CYBMUJFWSA-N [(2r)-heptan-2-yl] 4-methylbenzenesulfonate Chemical compound CCCCC[C@@H](C)OS(=O)(=O)C1=CC=C(C)C=C1 YNJWKWKTYUQIEO-CYBMUJFWSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 208000003464 asthenopia Diseases 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000003098 cholesteric effect Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- IPIVAXLHTVNRBS-UHFFFAOYSA-N decanoyl chloride Chemical compound CCCCCCCCCC(Cl)=O IPIVAXLHTVNRBS-UHFFFAOYSA-N 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 235000013367 dietary fats Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000010520 ghee Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- YECIFGHRMFEPJK-UHFFFAOYSA-N lidocaine hydrochloride monohydrate Chemical compound O.[Cl-].CC[NH+](CC)CC(=O)NC1=C(C)C=CC=C1C YECIFGHRMFEPJK-UHFFFAOYSA-N 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- REEZZSHJLXOIHL-UHFFFAOYSA-N octanoyl chloride Chemical compound CCCCCCCC(Cl)=O REEZZSHJLXOIHL-UHFFFAOYSA-N 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010288 sodium nitrite Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K19/126—Compounds containing at least one asymmetric carbon atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/121—Compounds containing phenylene-1,4-diyl (-Ph-)
- C09K2019/123—Ph-Ph-Ph
Abstract
Description
【発明の詳細な説明】
〔技術分野〕
本発明は新規な液晶性化合物並びにこの液晶性化合物を
少なくとも１種含有することを特徴とする液晶組成物に
関する。更に詳しく言えば本発明は強誘電性液晶に関し
、実用的な強誘電性液晶組成物作製の際、その組成成分
として有用で、かつ、化学的安定性に優れた新規なｐタ
ーフェニル１１導体並びにこのｐ−ターフェニル誘導体
の少なくとも１種を含有する液晶組成物に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a novel liquid crystal compound and a liquid crystal composition containing at least one such liquid crystal compound. More specifically, the present invention relates to ferroelectric liquid crystals, and relates to a novel p-terphenyl-11 conductor that is useful as a component in the production of practical ferroelectric liquid crystal compositions and has excellent chemical stability. The present invention relates to a liquid crystal composition containing at least one of the p-terphenyl derivatives.
時計、電卓、パーソナルワープロ、ポケットテレビ用等
の表示素子として、液晶表示素子は広く用いられている
。これらは、受光型で目が疲れない、消費電力が少ない
、薄型である等の優れた特徴を有しているが、一方にお
いては、応答速度が遅い、メモリー性がない等の点から
応用面において制限があった。応用面の拡大を図るため
、従来用いられていたツィステッドネマチック（ＴＮ）
型表示方式を改良したスーパーツィステッドネマチック
（ＳＴＮ）型表示方式等も提供されている。しかし、こ
れらは大画面表示用或いはグラフィック表示用としては
充分ではなく、従来これらに代わる液晶表示素子につい
ての研究も種々行われている。Liquid crystal display elements are widely used as display elements for watches, calculators, personal word processors, pocket televisions, and the like. These have excellent features such as light-receiving type that does not cause eye strain, low power consumption, and thinness. There were restrictions on Twisted nematic (TN), which was conventionally used, in order to expand the range of applications.
A super twisted nematic (STN) type display system, which is an improved type display system, has also been provided. However, these are not sufficient for large screen display or graphic display, and various studies have been conducted on liquid crystal display elements to replace them.
その１つに強誘電性液晶（Ｒ，Ｂ、 Ｍｅｙｅｒら；Ｐ
ｈｙｓｉｑｕｅ、 ３６ Ｌ−６９（１９７５））を利
用した表示方式（Ｎ、 Ａ、 Ｃ１ａｒｋら； Ａ
ｐｐｌｉｅｄ Ｐｈｙｓ、 １ｅｔｔ、、３６゜８９
９ （１９８０））がある。One of them is ferroelectric liquid crystals (R, B, Meyer et al.; P
hysique, 36 L-69 (1975))) (N, A, C1ark et al.; A
pplied Phys, 1ett, 36°89
9 (1980)).
この方式は従来方式に比べて１００倍もの高速応答であ
ること、及びメモリー性があること等の点で優れた特徴
を有しているため、液晶表示素子の用途拡大が期待され
ている。強誘電性液晶とは、液晶分子長軸が層法線方向
とある角度を有する一連のスメクチック液晶のことであ
るが、実用的にはカイラルスメクチックＣ（ＳＩＩＩＣ
本）相が用いられている。This method has excellent features such as a response time 100 times faster than conventional methods and memory performance, and is therefore expected to expand the use of liquid crystal display elements. Ferroelectric liquid crystals are a series of smectic liquid crystals in which the long axes of liquid crystal molecules form a certain angle with the layer normal direction.
This phase is used.
実用的には、多数の強誘電性液晶化合物から成る液晶組
成物として、又はスメクチックＣ（ＳＩＩＩＣ）相を有
する化合物或いはそれらの混合物に強誘電性液晶化合物
を添加して成る液晶組成物として用いられる。この場合
に、実用的なネマチック液晶表示素子作製の場合と同様
に、実用面において要求される種々の特性すなわち、動
作温度範囲、応答速度、自発分極、ラセンピッチ、化学
的安定性等を満足させるためには、多成分の混合が必要
とされる。Practically, it is used as a liquid crystal composition consisting of a large number of ferroelectric liquid crystal compounds, or as a liquid crystal composition consisting of a ferroelectric liquid crystal compound added to a compound having a smectic C (SIIIC) phase or a mixture thereof. . In this case, as in the case of manufacturing a practical nematic liquid crystal display element, in order to satisfy various characteristics required in practical terms, such as operating temperature range, response speed, spontaneous polarization, helical pitch, and chemical stability, etc. requires a multicomponent mixture.
従来技術によっては、強誘電性液晶組成物として未だ実
用に供せられるほどのものは見出されておらず、その組
成物の有用な成分となりうる種々の新規化合物の開発が
望まれている。Although conventional techniques have not yet found a ferroelectric liquid crystal composition that can be put to practical use, there is a desire to develop various new compounds that can be useful components of such compositions.
本発明者らは、特に強誘電性を示す温度範囲に視点を置
き、種々の新規構造を有する化合物をデザインし、合成
し、評価し、鋭意研究した結果、化学的に安定で、応答
速度に優れ、ＳｍＣ”相あるいは、ＳｍＣ相温度範囲の
広い新規化合物を提供することに成功した。The present inventors designed, synthesized, evaluated, and conducted extensive research on compounds with various new structures, with a particular focus on the temperature range that exhibits ferroelectricity. We have succeeded in providing a new compound with excellent SmC phase or a wide SmC phase temperature range.
すなわち、本発明は一般式
（Ｒ１およびＲ２は、それぞれ炭素原子数１−１８の直
鎖状又は分岐鎖状のアルキル基を示し、Ｙ及びＺは、そ
れぞれ、単結合、０、ＣＯＯ又はＯＣＯを示し、Ｘｌ、
Ｘ、及びＸ、は、それぞれ、水素原子、フッ素原子又は
塩素原子を示す）で表されるｐ −ターフェニル誘導体
並びに、それらの化合物の少なくとも１種を含有するこ
とを特徴とする液晶組成物を提供するものである。本発
明に係わる新規化合物はそれ自身単独でも広い温度範囲
でＳｍＣ＊相を有するものであるが、それらの混合物あ
るいはそれらと他の液晶化合物あるいは液晶組成物との
混合物を調製することにより、さらにＳｍＣｍＣ電相温
度範囲張された強誘電性液晶組成物を得ることができる
。That is, the present invention is based on the general formula (R1 and R2 each represent a linear or branched alkyl group having 1 to 18 carbon atoms, and Y and Z each represent a single bond, 0, COO or OCO). Indicates, Xl,
A liquid crystal composition containing a p-terphenyl derivative represented by (X and X each represent a hydrogen atom, a fluorine atom, or a chlorine atom) and at least one of these compounds. This is what we provide. The novel compound of the present invention has an SmC* phase by itself in a wide temperature range, but by preparing a mixture thereof or a mixture of them and other liquid crystal compounds or liquid crystal compositions, it is possible to further form an SmCmC* phase. A ferroelectric liquid crystal composition having a wide electric phase temperature range can be obtained.
従って、本発明に係わる新規なｐ−ターフェニル誘導体
はそれ自体公知の合成手段を組合せて使用することによ
り製造することができる。Therefore, the novel p-terphenyl derivative according to the present invention can be produced by using a combination of synthetic methods known per se.
その製造方法については、以下に、合成経路を式示し、
実施例等を示すことにより更に詳しく説明する。なお、
合成した化合物の相転移温度は測定機器、測定方法の違
い、或いは純度により影響されるため、その数値に多少
の異同が認められることは理解されよう。本発明に係る
新規なｐ−ターフェニル誘導体は種々の経路で合成する
ことができるが、その例を式示する。Regarding its production method, the synthetic route is shown below,
This will be explained in more detail by showing examples and the like. In addition,
It will be understood that the phase transition temperatures of synthesized compounds are affected by differences in measuring equipment, measuring methods, or purity, and therefore, there may be some differences in the values. The novel p-terphenyl derivative according to the present invention can be synthesized by various routes, examples of which are shown below.
式示した合成経路について以下に説明する。The synthetic route shown in the formula will be explained below.
４−アルキルオキシ−４“−アルキルオキシ−ｐ−ター
フェニル及びその誘導体（Ｉ−４）は、４−ブロムビフ
ェニル及びその誘導体を出発物質とし、アセチル化、バ
イヤービリガー酸化、加水分解、エーテル化反応を行っ
た後、４−アルキルオキシブロムベンゼン及びその誘導
体から調製したグリニヤール試薬とのクロスカップリン
グ反応を行うことによって合成することができる。また
、４−アルキルオキシカルボニル−４“−アルキル−ｐ
−ターフェニル及びその誘導体（ｌ−１４）は、４−ブ
ロムビフェニル及びその誘導体を出発物質とし、アシル
化、還元、ブロムベンゼン及びその誘導体から調製した
グリニヤール試薬とのクロスカップリング反応、アセチ
ル化、ハロホルム酸化、エステル化反応を行うことによ
って合成できる。また、４−アシルオキシ−４“−アル
キルオキシカルボニル−ｐ−ターフェニル及びその誘導
体（ＩＩ−４）は、アニソール及びその誘導体を出発物
質とし、臭素化、エーテルの開裂、ベンジルエーテル化
を行った後、グリニヤール試薬とし、４−ブロム−４′
−アルキルオキシカルボニルビフェニル及びその誘導体
とクロスカップリング反応ヲ行った後、エーテルの開裂
、エステル化反応を行うことによって合成することがで
きる。その他の合成経路式不例中に示した目的化合物（
Ｉ−１゜１−２、Ｉ−３、Ｉ−５、Ｉ−６、Ｉ−７、■
−８、Ｉ−９、ｌ−１０、Ｉ −１１，ｌ−１２、ｌ−
１３、Ｉ−１，ｕ−２、■−３）は、各工程において、
前記の諸反応を種々組み合わせて行うことによって合成
することができる。4-Alkyloxy-4"-alkyloxy-p-terphenyl and its derivatives (I-4) are produced by acetylation, Bayer-Villiger oxidation, hydrolysis, and etherification reactions using 4-brombiphenyl and its derivatives as starting materials. After that, it can be synthesized by carrying out a cross-coupling reaction with a Grignard reagent prepared from 4-alkyloxybromobenzene and its derivatives.Also, 4-alkyloxycarbonyl-4"-alkyl-p
- Terphenyl and its derivatives (l-14) are prepared by using 4-brombiphenyl and its derivatives as starting materials, acylation, reduction, cross-coupling reaction with Grignard reagent prepared from bromobenzene and its derivatives, acetylation, It can be synthesized by performing haloform oxidation and esterification reactions. In addition, 4-acyloxy-4"-alkyloxycarbonyl-p-terphenyl and its derivatives (II-4) are obtained by using anisole and its derivatives as starting materials, and after performing bromination, ether cleavage, and benzyl etherification. , Grignard reagent, 4-bromo-4'
It can be synthesized by carrying out a cross-coupling reaction with -alkyloxycarbonylbiphenyl and its derivatives, followed by ether cleavage and esterification. The target compound shown in other synthetic route formula examples (
I-1゜1-2, I-3, I-5, I-6, I-7, ■
-8, I-9, l-10, I -11, l-12, l-
13, I-1, u-2, ■-3) in each step,
It can be synthesized by performing various combinations of the above reactions.
以下の実施例中に記載されている略記号は以下のとおり
の意味を有する。The abbreviations described in the following examples have the following meanings.
ＧＬＣ： ガスクロマトグラフィーＨＰＬＣ：
高速液体クロマトグラフィー■Ｒ： 赤
外線吸収スペクトルＭａｓｓ ： 質量分析
ｍ、 ｐ・ ： 融点
Ｃ： 結晶
Ｓ８： 同定出来なかったスメクチック相Ｓ、
： スメクチックＢ相
５ｍＣ，Ｓｃ： スメクチックＣ相
ＳｍＣ本、Ｓｃ零：カイラルスメクチツクＣ相ＳＡ：
スメクチック人相
Ｃｈ： コレステリック相
■二 等方性液体
？： 温度不明
実施例 ｌ
還流撹拌下に、先に作成したジアゾニウム塩溶液を１時
間を要して滴下後、更に１時間反応させた。反応液を冷
却後、ヘキサン １１２を加えて抽出し、得られたヘキ
サン溶液を水、希苛性ソーダ水、水で順次洗浄し、芒硝
で脱水した後、ヘキサンを留去した残留物を減圧蒸留（
ｂ、 ｐ１３５〜１４２℃／ １５” １７ ｍ＋ｍＨ
ｇ） して４−ペンチルブロムベンゼン６１．５９ （
４４％）ヲ得り。GLC: Gas chromatography HPLC:
High performance liquid chromatography ■R: Infrared absorption spectrum Mass: Mass spectrometry m, p.: Melting point C: Crystal S8: Unidentified smectic phase S,
: Smectic B phase 5mC, Sc: Smectic C phase SmC, Sc zero: Chiral smectic C phase SA:
Smectic physiognomy Ch: Cholesteric phase ■2 Isotropic liquid? : Unknown temperature Example 1 The previously prepared diazonium salt solution was added dropwise over 1 hour while stirring under reflux, and the reaction was further allowed to proceed for 1 hour. After cooling the reaction solution, hexane 112 was added and extracted. The resulting hexane solution was sequentially washed with water, dilute caustic soda water, and water, and dehydrated with Glauber's salt. The hexane was distilled off and the residue was distilled under reduced pressure (
b, p135~142℃/15” 17 m+mH
g) 4-pentylbromobenzene61.59 (
44%) I got it.
ＧＬＣ９６％
「
反応器に４−ペンチルアニリン １００９及び水６００
＋ＩＩＱを仕込み、氷水冷撹拌下に濃硫酸８０ｇを滴下
し、次いで一５℃以下で亜硝酸ソーダ４３９の水８０ｒ
ａＱ溶液を滴下後、同温度で２時間撹拌反応してジアゾ
ニウム塩溶液を作成した。別の反応器に硫酸銅５水和物
（ＣｕＳＯ４”５ＨｘＯ） ３８．５ｇ、銅粉１２．２
９臭化ナトリウム ７０９及び水６００ｍＩ２を仕込み
、室温撹拌下に濃硫酸１８．５９次いで亜硫酸ソーダ７
水和物 ４．５ｇを添加し、これを昇温して反応器にマ
グネシウム末 ３．３ｇとヨウ素の小片を仕込み、これ
に上記（ａ）で得た４−ペンチルブロムベンゼン２２．
７９のテトラヒドロフラン（ＴＨＦ） ５０ｍｇ溶液の
少量を添加し、加熱撹拌した。GLC96% 4-pentylaniline 1009 and water 600 in the reactor
+IIQ was added, 80 g of concentrated sulfuric acid was added dropwise with stirring under ice-water cooling, and then 80 r of water containing 439 ml of sodium nitrite was added at -5°C or below.
After the aQ solution was added dropwise, the mixture was stirred and reacted at the same temperature for 2 hours to prepare a diazonium salt solution. In another reactor, 38.5 g of copper sulfate pentahydrate (CuSO4”5HxO), 12.2 g of copper powder
9 Sodium bromide 709 and water 600 mI2 were charged, and while stirring at room temperature, concentrated sulfuric acid 18.59 and then sodium sulfite 7
Add 4.5 g of hydrate, raise the temperature, charge 3.3 g of magnesium powder and a small piece of iodine into the reactor, and add 2.2 g of 4-pentylbromobenzene obtained in (a) above.
A small amount of a 50 mg solution of 79 in tetrahydrofuran (THF) was added, and the mixture was heated and stirred.
発泡して反応を開始してから残りの前記ＴＨＦ溶液を還
流を保つように滴下し、滴下後さらに２時間還流撹拌し
てグリニヤール試薬を作成した。After the reaction started with foaming, the remaining THF solution was added dropwise while maintaining reflux, and after the dropwise addition, the solution was further stirred under reflux for 2 hours to prepare a Grignard reagent.
別の反応器にジクロルビストリフェニルホスフィンパラ
ジウム（ＣＬＰｄ（ＰＰｈｓ）＊） ０．５９及びＴＨ
Ｆ３０ｍＱを仕込み、これにジイソブチルアルミニウム
ハイドライド（（ｉｓｏ−Ｃ＊Ｈｓ）ｔＡ（２Ｈ）の１
Ｍヘキサン溶液１．５ｍ１２を添加し、次いで室温撹拌
下に４−ブロム−２−フルオロビフェニル１９．５９の
ＴＨＦ９０ｍｆｆ溶液を加え、６０℃に昇温後、先に得
たグリニヤール試薬を滴下し、滴下後２時間熟成した。In a separate reactor dichlorbistriphenylphosphinepalladium (CLPd(PPhs)*) 0.59 and TH
Charge F30mQ, add 1 of diisobutylaluminum hydride ((iso-C*Hs)tA(2H))
Add 1.5 ml of M hexane solution, then add a THF 90 mff solution of 4-bromo-2-fluorobiphenyl 19.59 while stirring at room temperature, and after raising the temperature to 60 ° C., dropwise add the previously obtained Grignard reagent. It was then aged for 2 hours.
反応液を塩酸と氷水の４００ｒａＱ液に注加し、ベンゼ
ンで抽出後、飽和食塩水で洗液が中性になるまで洗浄し
、芒硝で脱水した。得られたベンゼン溶液を蒸留して溶
媒を留去し、残留分を減圧蒸留して得られた留分（ｂ、
ｐ １９８〜２０８℃１０．６ｎ＋ｍＨｇ）をヘキサン
で再結晶して４−ペンチル−３′−フルオロ−ｐ−ター
フェニル１２．０ｇ（４８，５％）を得た。The reaction solution was poured into a 400 raQ solution of hydrochloric acid and ice water, extracted with benzene, washed with saturated brine until the washings became neutral, and dehydrated with sodium sulfate. The obtained benzene solution was distilled to remove the solvent, and the residue was distilled under reduced pressure to obtain a fraction (b,
p 198-208° C. 10.6 n+mHg) was recrystallized from hexane to obtain 12.0 g (48.5%) of 4-pentyl-3'-fluoro-p-terphenyl.
ＧＬＣ９８，０％
反応器に塩化メチレン ３０１１Ｉ２及び無水塩化アル
ミニウム ７ｇを仕込み、撹拌下に０℃以下でアセチル
クロライド ５．６ｇを注加し、次いで上記（ｂ）で得
た４−ペンチル−３′−フルオロ−ｐ−ターフェニル
８．３３ｇの塩化メチレン ５０Ｉｌａ溶液を滴下後、
２時間同温度で撹拌反応させた。GLC98.0% Methylene chloride 3011I2 and 7 g of anhydrous aluminum chloride were charged into a reactor, and 5.6 g of acetyl chloride was added at below 0°C with stirring, followed by the 4-pentyl-3'- obtained in (b) above. Fluoro-p-terphenyl
After dropping 8.33 g of methylene chloride 50Ila solution,
The mixture was stirred and reacted at the same temperature for 2 hours.
反応液を冷希塩酸に注加し、ベンゼンで抽出後、飽和食
塩水、炭酸水素ナトリウム水溶液、飽和食塩水で順次洗
浄し、芒硝で脱水した後、溶媒を留去し、残留分をアセ
トンで再結晶して４−アセチル−２′−フルオロ−４＃
−ペンチル−ｐ−ターフェニル６．４５ｇ（６８，４％
）を得た。The reaction solution was poured into cold diluted hydrochloric acid, extracted with benzene, washed successively with saturated brine, sodium bicarbonate aqueous solution, and saturated brine, dehydrated with Glauber's salt, the solvent was distilled off, and the residue was reconstituted with acetone. Crystallized to 4-acetyl-2'-fluoro-4#
-Pentyl-p-terphenyl 6.45g (68.4%
) was obtained.
ＨＰＬＣ９７％
反応器に上記（Ｃ）で得た４−アセチル−２′−フルオ
ロ−４“−ペンチル−ｐ−ターフェニル６９及び塩化メ
チレン５０ｔａＱを仕込み、室温撹拌下に８８％ギｒａ
５０ｔａａ、無水酢酸 ２５禦ａ及び濃硫酸０．１
ｍｆｆを順次加え、更に３５％過酸化水素水 ７ｍ（ｔ
を１４℃で滴下した。滴下後４０℃で２４時間撹拌し反
応させ、反応液を氷水に注加し、ベンゼンで抽出後、希
塩酸次いで食塩水で洗浄し、芒硝で脱水した。得られた
ベンゼン溶液を蒸留し、ベンゼンを留去した残留分と、
エチルアルコール３００ｍＩ２及び３０％苛性カリ水溶
液５５ｍＱを反応器に仕込み、８時間還流撹拌した。反
応液を冷希塩酸中に注加し、ベンゼンで抽出し、食塩水
で洗浄し、芒硝で脱水した後、ベンゼンを留去して得ら
れた残留分をシリカゲルカラムクロマトグラフィー（溶
離液クロロホルム）で精製し、次いでメタノールで再結
晶して４−ヒドロキシ−２′−７ルオロー４＃−ペンチ
ル−ｐ−ターフェニル１．８９ （３２，４％）を得た
。HPLC 97% A reactor was charged with 69 4-acetyl-2'-fluoro-4"-pentyl-p-terphenyl obtained in (C) above and 50 taQ of methylene chloride, and 88% gira was added under stirring at room temperature.
50taa, acetic anhydride 25a and concentrated sulfuric acid 0.1
Add mff one by one, and then add 7 m (t) of 35% hydrogen peroxide solution.
was added dropwise at 14°C. After the dropwise addition, the mixture was stirred at 40° C. for 24 hours to react, and the reaction solution was poured into ice water, extracted with benzene, washed with dilute hydrochloric acid and then with brine, and dehydrated with sodium sulfate. The obtained benzene solution is distilled, and the residue obtained by distilling off the benzene,
300 mI2 of ethyl alcohol and 55 mQ of 30% aqueous potassium hydroxide solution were charged into a reactor and stirred under reflux for 8 hours. The reaction solution was poured into cold dilute hydrochloric acid, extracted with benzene, washed with brine, and dehydrated with sodium sulfate.The benzene was distilled off, and the resulting residue was subjected to silica gel column chromatography (eluent: chloroform). The product was purified and then recrystallized from methanol to obtain 1.89 (32.4%) of 4-hydroxy-2'-7-fluoro-4#-pentyl-p-terphenyl.
ＨＰＬＣ９９，５％
反応器に上記（ｄ）で得た４−ヒドロキシ−２′−フル
オロ−４＃−ペンチル−ｐ−ターフェニル０．６９．
（Ｓ） −２−メチルブチルブロマイド １ｇ。HPLC 99.5% 4-Hydroxy-2'-fluoro-4#-pentyl-p-terphenyl obtained in (d) above 0.69.
(S) -2-Methylbutyl bromide 1g.
炭酸カリウム０．８ｇ及び２−ブタノン（ＭＥＫ） １
０ｖｉＱを仕込み、還流撹拌下に１６時間反応させた。Potassium carbonate 0.8g and 2-butanone (MEK) 1
0viQ was charged, and the mixture was reacted for 16 hours under reflux and stirring.
反応液を、希塩酸に注加し、ベンゼンで抽出し、水洗し
、芒硝で脱水した後溶媒を留去し、残留分をシリカゲル
カラムクロマトグラフィー（溶離液ヘキサン：ベンゼン
−４：１）にて精製しくＳ）−４−（２−メチルブチル
）オキシ−２′−フルオロ−４“−ペンチル−ｐ−ター
フェニル０．３ｇ（４１，７％）を得た。The reaction solution was poured into dilute hydrochloric acid, extracted with benzene, washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent: hexane:benzene - 4:1). 0.3 g (41.7%) of S)-4-(2-methylbutyl)oxy-2'-fluoro-4"-pentyl-p-terphenyl was obtained.
この物の純度はＨＰＬＣで９８％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４０４に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 98% or higher by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 404 in R and Mass analysis, and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 ２
実施例１の（ｅ）における（Ｓ）−２−メチルブチルブ
ロマイド １ｇに替えて（Ｓ）−４−メチルヘキシルブ
ロマイド０．３６９を用い、他は実施例１と同様に操作
して得られた物質をアセトンで再結晶Ｌ、（Ｓ）−４−
（４−メチルヘキシル）オキシ−２′−フルオロ−４＃
−ペンチル−ｐ−ターフェニル０．４８９ （６１，９
％）を得た。Example 2 The same procedure as in Example 1 was carried out except that 0.369 g of (S)-2-methylbutyl bromide in (e) of Example 1 was replaced with 0.369 g of (S)-4-methylhexyl bromide. The obtained substance was recrystallized with acetone L, (S)-4-
(4-methylhexyl)oxy-2'-fluoro-4#
-pentyl-p-terphenyl 0.489 (61,9
%) was obtained.
この物の純度はＨＰＬ（：で９９％以上であった。また
ＩＲ及びＭａｓｓ分析で４３２に分子イオンピークが認
められたこと、並びに用いた原料からみて、得られた物
質が目的物であることを確認した。The purity of this product was 99% or higher by HPL (:). Also, a molecular ion peak was observed at 432 in IR and Mass analysis, and considering the raw materials used, the obtained substance was the desired product. It was confirmed.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 ３
実施例１の（６）における（Ｓ）−２−メチルブチルブ
ロマイド １９に替えて（Ｓ）−１−メチルへブチルト
シレート２．０ｇを用い、他は実施例１と同様に操作し
て（Ｒ）−４−（１−メチルヘプチル）オキシ−２′−
フルオロ−４１−ペンチル−ｐ−ターフェニル０．５９
（６２，５％）を得た。Example 3 In place of (S)-2-methylbutyl bromide 19 in (6) of Example 1, 2.0 g of (S)-1-methylhebutyl tosylate was used, and the other operations were the same as in Example 1. (R)-4-(1-methylheptyl)oxy-2'-
Fluoro-41-pentyl-p-terphenyl 0.59
(62.5%) was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４４６に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 446 in R and Mass analysis and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ’８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP'82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 ４
反応器に無水塩化アルミニウム １１３ｇ及び塩化メチ
レン６００ｍａを仕込み０°Ｃ以下で撹拌下にアセチル
クロライド １１３９を滴下し、次いで４−プロムー２
−フルオロビフェニル １００ｇの塩化メチレン４００
ｍｆｆ溶液を滴下した後、徐々に室温に戻しながら７時
間撹拌反応させた。反応液を氷と希塩酸中に注加し、塩
化メチレン層を水洗し、炭酸水素ナトリウム水溶液で洗
浄し、水洗し、芒硝で脱水した後溶媒を留去し、残留分
をアセトンで再結晶して４−アセチル−２′−フルオロ
ー４′−ブロムビフェニル９６９ （８２，２％）を得
た。Example 4 113 g of anhydrous aluminum chloride and 600 molar of methylene chloride were placed in a reactor, and acetyl chloride 1139 was added dropwise under stirring at 0°C or below, and then 4-promu2
-Fluorobiphenyl 100g methylene chloride 400
After the mff solution was added dropwise, the mixture was stirred and reacted for 7 hours while gradually returning to room temperature. The reaction solution was poured into ice and diluted hydrochloric acid, and the methylene chloride layer was washed with water, washed with an aqueous sodium bicarbonate solution, washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was recrystallized with acetone. 4-Acetyl-2'-fluoro-4'-brombiphenyl 969 (82.2%) was obtained.
ＧＬＣ１００％
カゲル力ラムクロマトグラフイー（溶離液ベンゼン）に
て精製し、４−ヒドロキシ−２′−フルオロ−４′−ブ
ロムビフェニル２８．１ｇ（４７，５％）を得た。The product was purified by GLC 100% Kagel's column chromatography (eluent benzene) to obtain 28.1 g (47.5%) of 4-hydroxy-2'-fluoro-4'-brombiphenyl.
反応器に上記（ａ）で得た４−アセチル−２′フルオロ
−４′−ブロムビフェニル６５ｇ及び塩化メチレン３０
０ｍＱを仕込み、１０℃で撹拌下に８８％ギ酸５００ｍ
（２、無水酢酸４８０ｍＱを滴下し、さらに濃硫酸 １
．５ｍ（２を加えた後、３５％過酸化水素水１５０＋１
＋を３時間を要して滴下し、滴下後、徐々に昇温して４
５〜５０℃で３０時間撹拌反応させた。65 g of 4-acetyl-2'fluoro-4'-brombiphenyl obtained in (a) above and 30 g of methylene chloride were placed in a reactor.
Add 0 mQ of 88% formic acid and 500 m of 88% formic acid under stirring at 10°C.
(2. Add 480 mQ of acetic anhydride dropwise, then add concentrated sulfuric acid 1
．． 5m (after adding 2, 35% hydrogen peroxide solution 150+1
+ was added dropwise over a period of 3 hours, and after dropping, the temperature was gradually raised to 4
The reaction was stirred at 5 to 50°C for 30 hours.
反応液を、氷水に注加し、ベンゼンで抽出し、炭酸水素
ナトリウム水溶液で洗浄し、水洗し、芒硝脱水を行い、
溶媒を留去し、残留分を得た。The reaction solution was poured into ice water, extracted with benzene, washed with an aqueous sodium bicarbonate solution, washed with water, and dehydrated with sodium sulfate.
The solvent was distilled off to obtain a residue.
この残留分とエチルアルコール２１２を別の反応器に仕
込み、これに２５％苛性カリ水溶液を加え、８時間還流
撹拌しｊ；。反応液を氷と希塩酸中に注加しベンゼンで
抽出し、食塩水で洗浄し、芒硝で脱水した後、溶媒を留
去し、残留分をシリ反応器に上記（ｂ）で得た４−ヒド
ロキシ−２′−フルオロ−４′−ブロムビフェニル ５
９．（Ｓ）−２−メチルブチルブロマイド ６．８ｇ、
炭酸カリウム ４９及び２−ブタノ７ （ＭＥＫ） ５
０ｍＱを仕込み、撹拌還流下に８時間反応させた。反応
液を希塩酸に注加し、ベンゼンで抽出し、水洗し、芒硝
で脱水した後、溶媒を留去し残留分をガラスチュウプオ
ーブン（ＧＴＯ）にて蒸留して得られる留分（ＧＴＯ設
定温度１４０’ｏ ／ ０．２ ｍｍＨｇ）をシリカゲ
ルカラムクロマトグラフィー（溶離液ヘキサン：ベンゼ
ン−４：ｌ）で精製し、（Ｓ）−４−（２−メチルブチ
ル）オキシ−２′−フルオロ−４′−ブロムビフェニル
４．５４９ （７２，０％）を得た。This residue and ethyl alcohol 212 were charged into a separate reactor, a 25% caustic potassium aqueous solution was added thereto, and the mixture was stirred under reflux for 8 hours. The reaction solution was poured into ice and diluted hydrochloric acid, extracted with benzene, washed with brine, and dehydrated with sodium sulfate. The solvent was distilled off, and the residue was transferred to a silica reactor to extract the 4-4-hydrochloride obtained in (b) above. Hydroxy-2'-fluoro-4'-brombiphenyl 5
9. (S)-2-methylbutyl bromide 6.8g,
Potassium carbonate 49 and 2-butano 7 (MEK) 5
0 mQ was charged and reacted for 8 hours under stirring and reflux. The reaction solution was poured into dilute hydrochloric acid, extracted with benzene, washed with water, and dehydrated with sodium sulfate. The solvent was distilled off and the residue was distilled in a glass tube oven (GTO) to obtain a fraction (GTO setting). (temperature 140'o/0.2 mmHg) was purified by silica gel column chromatography (eluent hexane:benzene-4:l) to obtain (S)-4-(2-methylbutyl)oxy-2'-fluoro-4' -brombiphenyl 4.549 (72.0%) was obtained.
ＴＬＣモノスポット
反応器にオクチルブロマイド２２．３ｇ、 ｐ−ブロム
フェノール２０ｇ、炭酸カリウム３３．３ｇ及び２−ブ
タ、ｔ ン（ＭＥＫ） ２００ｍ（２を仕込み、還流撹
拌下に１０時間反応した。反応液を希塩酸に注加し、ベ
ンゼンで抽出し、食塩水で洗浄し、芒硝で脱水した後、
溶媒を留去し、残留分を減圧蒸留し４−オクチルオキシ
ブロムベンゼン ２２．０ｇ（６６，８％）を得た。A TLC monospot reactor was charged with 22.3 g of octyl bromide, 20 g of p-bromophenol, 33.3 g of potassium carbonate, and 200 m of 2-butane (MEK), and reacted for 10 hours with stirring at reflux.The reaction solution was poured into dilute hydrochloric acid, extracted with benzene, washed with brine, and dehydrated with sodium sulfate.
The solvent was distilled off, and the residue was distilled under reduced pressure to obtain 22.0 g (66.8%) of 4-octyloxybromobenzene.
ｃｔ、ｃ ９９．８％
ｂ、 ｐ １２４〜１２７°Ｃ／ ０．２ ｍｍＨｇ
合成
反応器にマグネシウム末 ０．４ｇ及びヨウ素の小片を
仕込み、上記（ｄ）で得た４−オクチルオキシブロムベ
ンゼン ３．４９のＴＨＦ ２０ｍ（ｌ溶液の少量を加
え反応させる。次いで残りのＴＨＦ溶液を、還流を保ち
ながら撹拌下に滴下した後、更に２時間還流撹拌し、グ
リニヤール試薬を作成した。ct, c 99.8% b, p 124-127°C/0.2 mmHg
Charge 0.4 g of magnesium powder and a small piece of iodine into a synthesis reactor, add a small amount of 20 m (l) of THF solution of 3.49 4-octyloxybromobenzene obtained in (d) above, and react. Then, add the remaining THF solution. was added dropwise while stirring while maintaining reflux, and the mixture was further stirred under reflux for 2 hours to prepare a Grignard reagent.
別の反応容器に窒素気流下、ジクロロビストリフェニル
ホスフィンパラジウム
（ＣＩ２ｉＰｄ（ＰＰｈｓ）ｘ）０．１ｇ、 ＴＨＦ
２０ｒｔｒＱ、ジイソブチルアルミニウムハイドライド
（（ｉｓｏ−Ｃ，Ｈｇ）２ＡＩ２旧の１モルヘキサン溶
液０．５ｍ１２及び上記（ｃ）で得た（Ｓ）−４−（２
−メチルブチル）オキシ−２′−フルオロ−４′−ブロ
ムビフェニル ２ｇのＴＨＦ ２０ｍａ溶液を順次仕込
み、撹拌下に５０℃で先に作成したグリニヤール試薬を
滴下し、滴下後、同温度で６時間撹拌反応させた。反応
液を希塩酸に注加し、ベンゼンで抽出し、食塩水で洗浄
し、芒硝で脱水した後、溶媒を留去し、残留分をシリカ
ゲルカラムクロマトグラフィー（溶離液ヘキサン：ベン
ゼン−６：ｌ）にて精製し、さらにアセトンで再結晶し
、（Ｓ）−４−（２−メチルブチル）オキシ−２′−フ
ルオロ−４＃−才クチルオキシ−ｐ−ターフェニル１．
６２ｇ（５９，１％）を得た。In a separate reaction vessel under a nitrogen stream, 0.1 g of dichlorobistriphenylphosphine palladium (CI2iPd(PPhs) x) and THF were added.
20rtrQ, diisobutylaluminum hydride ((iso-C,Hg)2AI2 and 0.5ml of a 1 molar hexane solution of (S)-4-(2) obtained in (c) above)
-Methylbutyl)oxy-2'-fluoro-4'-brombiphenyl 2g of THF 20ma solution was sequentially charged, and the previously prepared Grignard reagent was added dropwise at 50°C with stirring. After the dropwise addition, the reaction was stirred at the same temperature for 6 hours. I let it happen. The reaction solution was poured into diluted hydrochloric acid, extracted with benzene, washed with brine, and dehydrated with sodium sulfate. The solvent was distilled off and the residue was subjected to silica gel column chromatography (eluent: hexane:benzene-6:l). and further recrystallized from acetone to give (S)-4-(2-methylbutyl)oxy-2'-fluoro-4#-cutyloxy-p-terphenyl.
62 g (59.1%) were obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４６２に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 462 in R and Mass analysis and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 ５
実施例４の（Ｃ）における（Ｓ）−２−メチルブチルブ
ロマイド６．８９に替えて（Ｓ）−４−メチルヘキシル
ブロマイド ４．０ｇを用い、他は実施例４と同様に操
作して（Ｓ）−４−（４−メチルヘキシル）オキシ−２
′−フルオロ−４′−ブロムビフェニル４．４７ｇ（６
５，４％）を得た（ＧＴＯ設定温度１６り℃／ ０．２
５ｍｍＨｇ）。Example 5 4.0 g of (S)-4-methylhexyl bromide was used instead of 6.89 g of (S)-2-methylbutyl bromide in (C) of Example 4, and the other procedures were the same as in Example 4. (S)-4-(4-methylhexyl)oxy-2
'-Fluoro-4'-brombiphenyl 4.47g (6
5.4%) was obtained (GTO set temperature 16℃/0.2
5mmHg).
ＴＬＣモノスポット
の合成
実施例４の（ｅ）における（Ｓ）−４−（２−メチルブ
チル）オキシ−２′−フルオロ−４′−ブロムビフェニ
ルに替えて上記（ａ）で得た（Ｓ）−４−（４−メチル
ヘキシル）オキシ−２′−フルオロ−４′−ブロムビフ
ェニルを用い、他は実施例４と同様に操作して（Ｓ）−
４−（４−メチルヘキシル）オキシ−２′−フルオロ−
４＃−オクチルオキシ−ｐ−ターフェニル １．０６ｇ
（３９，５％）を得た。Synthesis of TLC Monospot In place of (S)-4-(2-methylbutyl)oxy-2'-fluoro-4'-brombiphenyl in (e) of Example 4, (S)- obtained in (a) above was used. (S)-
4-(4-methylhexyl)oxy-2'-fluoro-
4#-octyloxy-p-terphenyl 1.06g
(39.5%) was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４９０に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 490 in R and Mass analysis and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 ６
反応器に塩化メチレン ２０ｍｆｆ及び無水塩化アルミ
ニウム ３．２ｇを仕込み、撹拌下に一５℃以下でオク
タノイルクロライド ４ｇを加え、次いで４−ブロム−
２−フルオロビフェニル ３ｇの塩化メチレンｌ Ｏｍ
（２溶液を滴下した。Example 6 20 mff of methylene chloride and 3.2 g of anhydrous aluminum chloride were charged into a reactor, and 4 g of octanoyl chloride was added at -5°C or below while stirring, and then 4-bromo-
2-fluorobiphenyl 3 g methylene chloride l Om
(Two solutions were added dropwise.
滴下後、０℃以下で３時間撹拌反応し、−夜室温で放置
後、反応液を氷／希塩酸中に注加し、ベンゼンで抽出し
、ベンゼン溶液を水洗し、希アンモニア水処理、水洗及
び芒硝脱水を順次行い、ベンゼンを留去した残留分をア
セトンで再結晶して４−オクタノイル−２′−フルオロ
−４′−プロムビフェニル３．８ｇ（８４，２％）ヲ得
り。After dropping, the reaction was stirred at 0°C or lower for 3 hours, and after being left at room temperature overnight, the reaction solution was poured into ice/diluted hydrochloric acid, extracted with benzene, the benzene solution was washed with water, treated with dilute ammonia water, washed with water, and After sequential dehydration of sodium sulfate and distillation of benzene, the residue was recrystallized with acetone to obtain 3.8 g (84.2%) of 4-octanoyl-2'-fluoro-4'-prombiphenyl.
丁ＬＣモノスポット
反応器に上記（ａ）で得た４−オクタノイル−２′−フ
ルオロ−４′−ブロムビフェニル３．７５９及びトリフ
ルオロ酢酸 ２０１１Ｉ２を仕込み、室温撹拌下にトリ
エチルシラン ２．４ｇを滴下し、６時間撹拌後、反応
液を水に注加し、ベンゼン抽出、水洗、炭酸水素ナトリ
ウム水溶液洗浄、水洗、芒硝脱水を順次行い、溶媒を留
去した後、ガラスチューブオーブン（ＧＴＯ）にて蒸留
し、４−オクチル−２′−フルオロ−４′−ブロムビフ
ェニル２．５６９（７１，１％）を得た。ＧＴＯ設定温
度１５０℃１０．２＋ｇ＋ｗＨｇ
ＴＬＣモノスポット
実施例４の（ｄ）におけるオクチルブロマイド２２．３
９に替えて、（Ｓ）−４−メチルヘキシルブロマイド２
０．７９を用い、他は実施例４と同様に操作して（Ｓ）
−４−（４−メチルヘキシル）オキシブロムベンゼン２
４．１９（７７％）１１：。3.759 4-octanoyl-2'-fluoro-4'-brombiphenyl obtained in (a) above and trifluoroacetic acid 2011I2 were placed in a Ding LC monospot reactor, and 2.4 g of triethylsilane was added dropwise while stirring at room temperature. After stirring for 6 hours, the reaction solution was poured into water, and sequentially extracted with benzene, washed with water, washed with an aqueous sodium bicarbonate solution, washed with water, and dehydrated with mirabilite. After distilling off the solvent, it was placed in a glass tube oven (GTO). Distillation gave 2.569 (71.1%) of 4-octyl-2'-fluoro-4'-brombiphenyl. GTO set temperature 150°C 10.2+g+wHg Octyl bromide in TLC monospot Example 4 (d) 22.3
9, (S)-4-methylhexyl bromide 2
0.79, and otherwise operated in the same manner as in Example 4 (S)
-4-(4-methylhexyl)oxybromobenzene 2
4.19 (77%) 11:.
ｂ、ｐ １２０〜１２３℃／ ０．５ ｍｍＨｇの合
成
反応器にマグネシウム末 ０゜２ｇ及びヨウ素の小片を
仕込み、上記（ｃ）で得た（Ｓ）−４−（４−メチルヘ
キシル）オキシブロムベンゼン １．３９のＴ）ｆＦ
１０ｍ（ｌ溶液の少量を加え反応させた。次いで、残り
のＴＨＦ溶液を還流を保つよう撹拌下に滴下した後、更
に、２時間還流撹拌しグリニヤール試薬を作成した。別
の反応容器に窒素気流下、ジクロルビストリフェニルホ
スフィンパラジウム（Ｃ（ｌｚＰｄ（ＰＰｈｘ）ｘ）
０．１９．ＴＨＦ １０ｍ＜２．ジイソブチルアルミ
ニウムハイドライド（（ｉｓｏ−Ｃ４Ｈ＠）ｘＡＩ２Ｈ
）の１モルヘキサン溶液０．５ｍｆｆ及び上記（ｂ）で
得た４−才クチル−２′−フルオロ−４′−ブロムビフ
ェニル １．７９のＴＨＦ １０ｍＱ溶液を順次仕込
み、撹拌下に５０℃で先に作成したグリニヤール試薬を
滴下し、滴下後間温度で６時間撹拌反応した。b, p 0.2 g of magnesium powder and a small piece of iodine were placed in a synthesis reactor at 120-123°C/0.5 mmHg, and (S)-4-(4-methylhexyl)oxybrome obtained in (c) above was prepared. Benzene 1.39 T) fF
A small amount of 10ml solution was added and reacted.Then, the remaining THF solution was added dropwise while stirring to maintain reflux, and the Grignard reagent was prepared by further refluxing and stirring for 2 hours.Into another reaction vessel, a nitrogen stream was added. Bottom, dichlorbistriphenylphosphine palladium (C(lzPd(PPhx)x)
0.19. THF 10m<2. Diisobutylaluminum hydride ((iso-C4H@)xAI2H
0.5 mff of a 1M hexane solution of ) and a 10 mQ THF solution of 1.79 of the 4-year-old ctyl-2'-fluoro-4'-brombiphenyl obtained in (b) above were charged in sequence, and the mixture was heated at 50°C under stirring. The prepared Grignard reagent was added dropwise, and after the addition, the reaction was stirred at room temperature for 6 hours.
反応液を希塩酸に注加し、ベンゼンで抽出し、食塩水で
洗浄し、芒硝で脱水した後、溶媒を留去し、残留分をシ
リカゲルカラムクロマトグラフィー（溶離液ヘキサン：
ベンゼン−６： １）にて精製し、さらにアセトンで再
結晶し、（Ｓ）−４−（４−メチルヘキシル）オキシ−
３′−フルオロ−４“−オクチル−ｐ−ターフェニル０
．３２９（１４，５％）を得た。The reaction solution was poured into diluted hydrochloric acid, extracted with benzene, washed with brine, and dehydrated with sodium sulfate. The solvent was distilled off, and the residue was subjected to silica gel column chromatography (eluent: hexane:
Benzene-6: Purified with 1) and further recrystallized with acetone to obtain (S)-4-(4-methylhexyl)oxy-
3'-Fluoro-4"-octyl-p-terphenyl 0
．． 329 (14.5%) was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４７４に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 474 in R and Mass analysis, and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 ７
反応器にｐ−ブロムフェノール １０ｇ、 （Ｓ） −
１−メチルへキシルオシレー） １９ｇ、炭酸カリウ
ム１０９並びにシクロへキサノン１５０ｍ１２を仕込み
、１５時間（ＧＬＣにて原料の消失を確認）撹拌還流し
た。反応液を濾過して得られた固形物をベンゼンで洗浄
し、この洗液と濾液を合わせ、水洗した後、芒硝で脱水
し、溶媒を留去した残留分をシリカゲルカラムクロマト
グラフィー（溶離液ヘキサン）で精製しくＲ）−４−（
１−メチルヘキシル）オキシブロムベンゼン１４９（８
９，４％）を得た。Example 7 10 g of p-bromophenol, (S) - in a reactor
19 g of 1-methylhexyl oxysilane), 109 g of potassium carbonate, and 150 m12 of cyclohexanone were charged, and the mixture was stirred and refluxed for 15 hours (disappearance of the raw materials was confirmed by GLC). The solid substance obtained by filtering the reaction solution was washed with benzene, the washing liquid and the filtrate were combined, washed with water, dehydrated with sodium sulfate, and the residue obtained by distilling off the solvent was subjected to silica gel column chromatography (eluent: hexane). ) to purify R)-4-(
1-Methylhexyl)oxybromobenzene 149(8
9.4%).
ＧＬＣ９８，４％
認められたこと、並びに用いた原料からみて、得られた
物質が目的物であることを確認した。Considering the fact that GLC98.4% was observed and the raw materials used, it was confirmed that the obtained substance was the desired product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 ８
実施例４（ｅ）における４−オクチルオキシブロムベン
ゼン ３．４ｇに替えて上記（ａ）で得た（Ｒ）−４−
（１−メチルヘキシル）オキシブロムベンゼン３．２ｇ
を用い、また（Ｓ）−４−（２−メチルブチル）オキシ
−２′−フルオロ−４’−’ロムビフェニル ２ｇに替
えて実施例６（ｂ）で得られる４−オクチル−２′−フ
ルオロ−４′−ブロムビフェニル ２．２ｇを用い、他
は実施例４と同様に操作して（Ｒ）−４−（１−メチル
ヘキシル）オキシ−３′−フルオロ−４“−オクチル−
ｐ−ターフェニル０．３１ｇ（１１％）を得を二。Example 8 In place of 3.4 g of 4-octyloxybromobenzene in Example 4(e), (R)-4- obtained in the above (a) was used.
(1-methylhexyl)oxybromobenzene 3.2g
and 4-octyl-2'-fluoro- obtained in Example 6(b) in place of 2 g of (S)-4-(2-methylbutyl)oxy-2'-fluoro-4'-'rombiphenyl. (R)-4-(1-methylhexyl)oxy-3'-fluoro-4"-octyl-
0.31 g (11%) of p-terphenyl was obtained.
この物の純度はＨＰＬＣで９８％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４７４に分子イオンピークが実施
例４（ｃ）における（Ｓ）−２−メチルブチルブロマイ
ド ６．８ｇに替えてヘキシルブロマイド６ｇを用い、
他は実施例４と同様に操作し、後旭理を行って得られた
粗生成物をガラスチューブオーブン（ＧＴＯ）にて蒸留
し４−へキシルオキシ−２′−フルオロ−４′−ブロム
ビフェニル５．８ｙ （８８，３％）を得た。ＧＴＯ設
定温度１５０℃１０．１５ｍｍＨｇ
実施例４（ｅ）における４−才クチルオキシブロムベン
ゼン３．４ｇに替えて実施例７（ａ）で得られる（Ｒ）
−４−（１−メチルヘキシル）オキシブロムベンゼン３
ｇを用い、又、（Ｓ）−４−（２−メチルブチル）オキ
シ−２′−フルオロ−４′−ブロムビフェニル２９に替
えて、上記（ａ）で得た４−へキシルオキシ−２′−フ
ルオロ−４′−ブロムビフェニル２ｇを用い、他は実施
例４と同様に操作して（Ｒ）−４−（１−メチルヘキシ
ル）オキシ−３′−フルオロ−４＃−へキシルオキシ−
ｐ−ターフェニル０．４９ （１５％）を得た。The purity of this product was 98% or higher by HPLC. Also I
R and Mass analysis showed a molecular ion peak at 474 using 6 g of hexyl bromide in place of 6.8 g of (S)-2-methylbutyl bromide in Example 4(c),
Other operations were carried out in the same manner as in Example 4, and the resulting crude product was distilled in a glass tube oven (GTO) and 4-hexyloxy-2'-fluoro-4'-brombiphenyl .8y (88.3%) was obtained. GTO set temperature 150°C 10.15 mmHg (R) obtained in Example 7(a) in place of 3.4 g of 4-year-old ctyloxybromobenzene in Example 4(e)
-4-(1-methylhexyl)oxybromobenzene 3
g, and replacing (S)-4-(2-methylbutyl)oxy-2'-fluoro-4'-brombiphenyl 29 with 4-hexyloxy-2'-fluoro obtained in (a) above. (R)-4-(1-methylhexyl)oxy-3'-fluoro-4#-hexyloxy-
0.49 (15%) of p-terphenyl was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４６２に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 462 in R and Mass analysis and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 ９
反応器に実施例４（ｂ）で得られる４−ヒドロキシ−２
７−ｙルオロ−４′−ブロムビフェニル１２９、デシル
ブロマイド １４．２９．炭酸カリウム１５．７９並び
に２−ブタノン（ＭＥＫ） １００ｍ１２を仕込み、１
２時間（ＴＬＣで原料の消失を確認）撹拌還流した。反
応液を希塩酸に注加し、ベンゼンで抽出し、水洗し、芒
硝で脱水した後、溶媒を留去し、残留分をシリカゲルカ
ラムクロマトグラフィー（溶離液ヘキサン）で精製し、
更にヘキサンで再結晶して４−デシルオキシ−２′−フ
ルオロ−４′−ブロムビフェニル １４．９ｇ（８１，
５％）を得た。Example 9 4-Hydroxy-2 obtained in Example 4(b) in a reactor
7-yfluoro-4'-brombiphenyl 129, decyl bromide 14.29. Charge 15.79 m of potassium carbonate and 100 m12 of 2-butanone (MEK),
The mixture was stirred and refluxed for 2 hours (disappearance of the raw material was confirmed by TLC). The reaction solution was poured into dilute hydrochloric acid, extracted with benzene, washed with water, and dehydrated with sodium sulfate. The solvent was distilled off, and the residue was purified by silica gel column chromatography (eluent: hexane).
Further recrystallization from hexane yielded 14.9 g of 4-decyloxy-2'-fluoro-4'-brombiphenyl (81,
5%).
合成
実施例７（ｂ）における４−オクチル−２′−フルオロ
−４′−ブロムビフェニル ２．２ｇに替えて（ａ）で
得た４−デシルオキシ−２′−フルオロ−４′−ブロム
ビフェニル２．４ｇを用い、他は実施例７と同様に操作
して（Ｒ）−４−（１−メチルヘキシル）オキシ−３′
−フルオロ−４＃−デシルオキシ−ｐ−ターフェニル０
．５５９（１８％）を得た。4-decyloxy-2'-fluoro-4'-brombiphenyl obtained in (a) in place of 2.2 g of 4-octyl-2'-fluoro-4'-brombiphenyl in Synthesis Example 7 (b). (R)-4-(1-methylhexyl)oxy-3'
-Fluoro-4#-decyloxy-p-terphenyl 0
．． 559 (18%) was obtained.
この物の純度はＨＰＬＣで９８％以上であった。またＩ
Ｒ及びＭａｓｓ分析で５１８に分子イオンビークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 98% or higher by HPLC. Also I
It was confirmed that a molecular ion peak was observed in 518 by R and Mass analysis, and in view of the raw materials used, the obtained substance was the desired product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 １０
実施例４（ｄ）におけるオクチルブロマイド２２．３ｇ
に替えてヘキシルブロマイド １９ｇを用い、他は実施
例４と同様に操作して４−へキシルオキシブロムベンゼ
ン２６．７９（８９，９％）ヲ得り。Example 10 22.3 g of octyl bromide in Example 4(d)
26.79 (89.9%) of 4-hexyloxybromobenzene was obtained in the same manner as in Example 4 except that 19 g of hexyl bromide was used instead of 19 g of hexyl bromide.
ｂ、 ｐ １０６〜１１５℃／ ０．５ ｍｍＨｇ実
施例４（ｃ）における（Ｓ）−２−メチルブチルブロマ
イド６．８９に替えて、（Ｒ）−１−メチルへキシルト
シレート ７．５ｇを用い、他は実施例４と同様に操作
し、後処理を行って得られた粗生成物をシリカゲルカラ
ムクロマトグラフィー（溶出液ヘキサン）で精製し、（
Ｓ）−４−（１−メチルヘキシル）オキシ−２′−フル
オロ−４′−ブロムビフェニル６．１９ （８９，３％
）ヲ得り。b, p 106-115°C/0.5 mmHg 7.5 g of (R)-1-methylhexyl tosylate was substituted for 6.89 of (S)-2-methylbutyl bromide in Example 4(c). The crude product obtained by post-treatment was purified by silica gel column chromatography (eluent: hexane).
S)-4-(1-methylhexyl)oxy-2'-fluoro-4'-brombiphenyl 6.19 (89.3%
) I got it.
合成
実施例４（ｅ）における４−オクチルオキシブロムベン
ゼン３．４ｇに替えて上記（ａ）で得た４−へキシルオ
キシブロムベンゼン ３ｇを用い、又、（Ｓ）−４−（
２−メチルブチル）オキシ−２′−フルオロ−４′−ブ
ロムビフェニル ２．０９に替工て上記（ｂ）で得た（
Ｓ）−４−（１−メチルヘキシル）オキシ−２′−フル
オロ−４′−ブロムビフェニル２．０ｇを用い、他は実
施例４と同様に操作して（Ｓ）−４−（１−メチルヘキ
シル）オキシ−２′−フルオロ−４＃−へキシルオキシ
−ｐ−ターフェニル０．２５９ （１０％）を得に。In place of 3.4 g of 4-octyloxybromobenzene in Synthesis Example 4(e), 3 g of 4-hexyloxybromobenzene obtained in the above (a) was used, and (S)-4-(
2-Methylbutyl)oxy-2'-fluoro-4'-brombiphenyl 2.09 was obtained in (b) above (
(S)-4-(1-methylhexyl)oxy-2'-fluoro-4'-brombiphenyl was used in the same manner as in Example 4 except that (S)-4-(1-methyl Hexyl)oxy-2'-fluoro-4#-hexyloxy-p-terphenyl 0.259 (10%) was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４６２に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 462 in R and Mass analysis and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 １１
実施例４（ｄ）におけるオクチルブロマイド２２．３９
に替えてデシルブロマイド２５．７９を用い、他は実施
例４と同様に操作して４−デシルオキシブロムベンゼン
３１．０ｇ（８５，８％）を得り。Example 11 Octyl bromide in Example 4(d) 22.39
The procedure was repeated in the same manner as in Example 4, except that 25.79 g of decyl bromide was used instead of 25.7 g of decyl bromide, to obtain 31.0 g (85.8%) of 4-decyloxybromobenzene.
ｂ、ｐ １３６〜１４６℃１０．２５ ｍＩＱＨｇ合
成
実施例４（ｅ）における４−オクチルオキシブロムベン
ゼン３．４ｇに替えて上記（ａ）で得た４−デシルオキ
シブロムベンゼン３．５ｇを用い、又、（Ｓ）−４−（
２−メチルブチル）オキシ−２′−フルオロ−４′−ブ
ロムビフェニル ２ｇに替えて実施例１０（ｂ）で得ら
れる（Ｓ）−４−（１−メチルヘキシル）オキシ−２′
−フルオロ−４′−ブロムビフェニル ２．０ｇを用い
、他は実施例４と同様に操作して、（Ｓ）−４−（１−
メチルヘキシル）オキシ−２７−ｙルオロー４“−デシ
ルオキシ−ｐ−ターフェニル０．４２９ （１４，８％
）を得た。b, p 136-146°C 10.25 mIQHg Using 3.5 g of 4-decyloxybromobenzene obtained in (a) above in place of 3.4 g of 4-octyloxybromobenzene in Synthesis Example 4(e), Also, (S)-4-(
(S)-4-(1-methylhexyl)oxy-2' obtained in Example 10(b) in place of 2 g of 2-methylbutyl)oxy-2'-fluoro-4'-brombiphenyl
-Fluoro-4'-brombiphenyl 2.0g was used, and the other operations were the same as in Example 4, (S)-4-(1-
Methylhexyl)oxy-27-yruol-4"-decyloxy-p-terphenyl 0.429 (14,8%
) was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で５１８に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 518 in R and Mass analysis, and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 １２
反応器に２−フルオロフェノール １０９． （Ｓ）−
１−メチルへキシルトシレート２５９． 炭酸カリウム
２０ｇ並びｌ： Ｍ Ｅ Ｋ ｌ ６０ ｖａ Ｑ ｔ
仕込ｈ、１４時間（ＴＬＣ″′ｃ原料の消失を確認）
還流撹拌した。反応液を希塩酸に注加し、ベンゼンで抽
出し、水洗し、芒硝で脱水した後、溶媒を留去し、残留
分を減圧蒸留して（Ｒ）−２−（１−メチルヘキシル）
オキシフルオロベンゼン １４９（７４，５％）ヲ得た
。Example 12 2-fluorophenol in reactor 109. (S)-
1-Methylhexyl tosylate 259. 20g of potassium carbonate lined up: M E K l 60 va Q t
Preparation h, 14 hours (TLC''c confirmed disappearance of raw materials)
The mixture was stirred at reflux. The reaction solution was poured into dilute hydrochloric acid, extracted with benzene, washed with water, dehydrated with sodium sulfate, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain (R)-2-(1-methylhexyl).
Oxyfluorobenzene 149 (74.5%) was obtained.
ｂ、 ｐ １１３〜１１７℃／９ｍｍＨｇ反応器に上
記（ａ）で得た（Ｒ）−２−（１−メチルヘキシル）オ
キシフルオロベンゼン １３．９ｇ並びにクロロホルム
５ｏｒｌｒＱを仕込み、室温撹拌下に臭素１２．７ｇ
を滴下し、さらに室温撹拌（ＧＬＣで原料の消失を確認
）した後、１０％苛性ソーダ水溶液を加えて撹拌した。b, p 13.9 g of (R)-2-(1-methylhexyl)oxyfluorobenzene obtained in (a) above and 5 orlrQ of chloroform were charged into a 113-117°C/9 mmHg reactor, and 12.5 g of bromine was added under stirring at room temperature. 7g
was added dropwise and further stirred at room temperature (disappearance of the raw material was confirmed by GLC), and then a 10% aqueous solution of caustic soda was added and stirred.
有機層を水洗し、芒硝で脱水し、溶媒を留去した残留分
を減圧蒸留して（Ｒ）−４−（１−メチルヘキシル）オ
キシ−３−フルオロブロムベンゼン １４．２ｇ（７４
，１％）を得た。The organic layer was washed with water, dehydrated with Glauber's salt, the solvent was distilled off, and the residue was distilled under reduced pressure to give 14.2 g (R)-4-(1-methylhexyl)oxy-3-fluorobrombenzene (74
, 1%).
ｂ、ｐ９８〜１１０℃１０．３ ｍｍＨｇ反応器に４
−ヒドロキシ−４′−ブロムビフェニル１５ｇ、オクチ
ルブロマイド１４９．炭酸カリ’７Ａ １６９並び４
：、ＭＥＫ １００＊ｆｆを仕込み、８時間（ＧＬＣ
で原料の消失を確認）撹拌還流した。反応液を濾過して
固形物を除いた濾液を濃縮して得られた残留分をアセト
ンで再結晶して４−オクチルオキシ−４′−ブロムビフ
ェニル１８９（９０％）を得た。b, p98-110℃ 10.3 mmHg reactor 4
-Hydroxy-4'-brombiphenyl 15g, octyl bromide 149. Potassium carbonate '7A 169 row 4
:, Prepare MEK 100*ff, 8 hours (GLC
(confirm the disappearance of the raw material) The mixture was stirred and refluxed. The reaction solution was filtered to remove solid matter, and the filtrate was concentrated, and the resulting residue was recrystallized with acetone to obtain 4-octyloxy-4'-brombiphenyl 189 (90%).
成
実施例４（ｅ）における４−オクチルオキシブロムベン
ゼン３．４ｇに替えて上記（Ｃ）で得た４−オクチルオ
キシ−４′−ブロムビフェニル ４．３ｇを用い、又、
（Ｓ）−４−（２−メチルブチル）オキシ−２′−フル
オロ−４′−ブロムビフェニル２．０ｇに替えて上記（
ｂ）で得た（Ｒ）−４−（１−メチルヘキシル）オキシ
−３−フルオロブロムベンゼン １，７ｇを用い、他は
実施例４と同様に操作して（Ｒ）−４−（１−メチルヘ
キシル）オキシ−３−フルオロ−４＃−オクチルオキシ
−ｐ−ターフェニル０．４７９ （１６％）を得た。In place of 3.4 g of 4-octyloxybrombenzene in Example 4 (e), 4.3 g of 4-octyloxy-4'-brombiphenyl obtained in the above (C) was used, and
(S)-4-(2-Methylbutyl)oxy-2'-fluoro-4'-brombiphenyl 2.0g was replaced with the above (
(R)-4-(1- 0.479 (16%) of methylhexyl)oxy-3-fluoro-4#-octyloxy-p-terphenyl was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４９０に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 490 in R and Mass analysis and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 １３
実施例１２（ｄ）における４−オクチルオキシ−４′−
ブロムビフェニル４．３９に替工て４−へブチル−４′
−ブロムビフェニル ３．９ｇを用い、他は実施例１２
と同様に操作して（Ｒ）−４−（１−メチルヘキシル）
オキシ−３−フルオロ−４１−へブチル−ｐ−ターフェ
ニル１．７９ （６２，１％）を得た。Example 13 4-octyloxy-4'- in Example 12(d)
4-Hebutyl-4' instead of brombiphenyl 4.39
- Brombiphenyl 3.9g was used, others were Example 12
Proceed in the same manner as (R)-4-(1-methylhexyl)
1.79 (62.1%) of oxy-3-fluoro-41-hebutyl-p-terphenyl was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４６０に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 460 in R and Mass analysis, and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 １４
実施例４（ｅ）における４−オクチルオキシブロムベン
ゼン３．４ｇに替えて実施例１２（ｂ）で得うれる（Ｒ
）−４−（１−メチルヘキシル）オキシ−３−フルオロ
ブロムベンゼン３．４９を用い、又、（Ｓ）−４−（２
−メチルブチル）オキシ−２′−フルオロ−４′−ブロ
ムビフェニル ２．０９に替工て実施例６（ｂ）で得ら
れる４−オクチル−２′−フルオロ−４′−ブロムビフ
ェニル２．２ｇを用い、他は実施例４と同様に操作して
（Ｒ）−４−（１−メチルヘキシル）オキシ−３，３′
−ジフルオロ−４＃−オクチル−ｐ−ターフェニル１．
３ｇ （４３，６％）を得た。Example 14 In place of 3.4 g of 4-octyloxybromobenzene in Example 4(e), (R
)-4-(1-methylhexyl)oxy-3-fluorobromobenzene (3.49%) and (S)-4-(2
-methylbutyl)oxy-2'-fluoro-4'-brombiphenyl 2.2 g of 4-octyl-2'-fluoro-4'-brombiphenyl obtained in Example 6(b) was used instead of 2.09. , and otherwise operated in the same manner as in Example 4 to prepare (R)-4-(1-methylhexyl)oxy-3,3'
-difluoro-4#-octyl-p-terphenyl1.
3 g (43.6%) were obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４９２に分子イオンピークが認め
られＩ；こと、並びに用いた原料からみて、得られた物
質が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
A molecular ion peak was observed at 492 in R and Mass analysis, and in view of the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 １５
実施例４（ｃ）における（Ｓ）−２−メチルブチルブロ
マイド ６．８ｇに替えてオクチルブロマイド５．２ｇ
を用い、他は実施例４と同様に操作し、後処理を行って
得られた粗生成物をシリカゲルカラムクロマトグラフィ
ー（溶離液へキサン）で精製し４−オクチルオキシ−２
′−フルオロ−４′−ブロムビフェニル６．３９ （８
８，７％）ヲ得り。Example 15 6.8 g of (S)-2-methylbutyl bromide in Example 4(c) was replaced with 5.2 g of octyl bromide.
4-octyloxy-2
'-Fluoro-4'-brombiphenyl6.39 (8
8.7%) I got it.
合成
実施例４（ｅ）における４−オクチルオキシブロムベン
ゼン３．４ｇに替えて実施例１２（ｂ）で得られる（Ｒ
）−４−（１−メチルヘキシル）オキシ−３−フルオロ
ブロムベンゼン３．４ｇヲ用い、又、（Ｓ）−４−（２
−メチルブチル）オキシ−２′−フルオロ−４′−ブロ
ムビフェニル ２ｇに替工て上記（ａ）で得た４−オク
チルオキシ−２′−フルオロ−４′−ブロムビフェニル
２．２ｇヲ用い、他ハ実施例４と同様に操作して（Ｒ
）−４−（１−メチルヘキシル）オキシ−３，３′−ジ
フルオロ−４＃−オクチルオキシーｐ−ターフェニル
０．５９ （１７％）を得た。Synthesis Example 4(e) in place of 3.4 g of 4-octyloxybromobenzene (R
)-4-(1-methylhexyl)oxy-3-fluorobromobenzene was used, and (S)-4-(2
-Methylbutyl)oxy-2'-fluoro-4'-brombiphenyl 2.2 g was used instead of 2.2 g of 4-octyloxy-2'-fluoro-4'-brombiphenyl obtained in (a) above, and other In the same manner as in Example 4, (R
)-4-(1-methylhexyl)oxy-3,3'-difluoro-4#-octyloxy-p-terphenyl
0.59 (17%) was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で５０８に分子イオンビークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
It was confirmed that a molecular ion peak was observed in 508 by R and Mass analysis, and that the obtained substance was the desired substance in view of the raw materials used.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 １６
反応器に４−ヒドロキシ−４′−ブロムビフェニル１．
１９．２−ブタノン２０ｒａＱ 、炭酸カリウム１．２
ｇ及び（Ｓ）−４−メチルヘキシルブロマイド０．９５
９を仕込み、ＴＬＣで原料が消失するまで撹拌還流した
。１０時間を要した。反応液を濾過して固形物を除き、
濾液を濃縮して得られる残留物を減圧乾燥しく５）−４
−（４−メチルヘキシル）オキシ−４′−ブロムビフェ
ニル１．４ｇ（９３％）ヲ得た。Example 16 4-Hydroxy-4'-brombiphenyl 1.
19.2-butanone 20raQ, potassium carbonate 1.2
g and (S)-4-methylhexyl bromide 0.95
9 was charged, and the mixture was stirred and refluxed until the starting material disappeared as determined by TLC. It took 10 hours. Filter the reaction solution to remove solids,
The residue obtained by concentrating the filtrate is dried under reduced pressure5)-4
1.4 g (93%) of -(4-methylhexyl)oxy-4'-brombiphenyl was obtained.
ＧＬＣ９６％
（ｂ） Ｃａ。Ｈ８１べ＝ΣＢ「の合成実施例１（ａ
）において、４−ペンチルアニリンに替えて４−デシル
アニリンを用い、他は実施例１と同様に操作して４−デ
シルブロムベンゼン４８．４９（３８％）を得た。GLC96% (b) Ca. Synthesis Example 1 (a
48.49 (38%) of 4-decylbromobenzene was obtained in the same manner as in Example 1 except that 4-decylaniline was used in place of 4-pentylaniline.
ｂ、 ｐ１３６〜１４１’ｏ ／ ０．４ ｍｍＨｇ合
成
反応器にマグネシウム末０．３５９とヨウ素の小片を仕
込み、これに上記（ｂ）で得た４−デシルブロムベンゼ
ン ４ｇのＴＨＦ １０ｍ１２溶液の少量を加え、発泡
して反応を開始させた。次いで残りの前記ＴＨＦ溶液を
還流を保つように撹拌下に滴下し、滴下後２時間還流撹
拌し、グリニヤール試薬を作成した。別の容器にジクロ
ルビストリフェニルホスフィンパラジウＡ（Ｃ（２ｔＰ
ｄ（ＰＰｈｓ）ｚ）５０ＩＩｇ及びＴＨＦ３＋ｍ（＋を
仕込み、これにジイソブチルアルミニウムハイドライド
（（ｉｓｏ−ＣａＨｓ）ｘＡＩ２Ｈ）の１Ｍヘキサン溶
液０．１ｍｆｆを加え、次いで上記（ａ）で得た（Ｓ）
−４−（４−メチルヘキシル）オキシ−４′−ブロムビ
フェニル１．４ｇのＴＨＦ ５ｍｆｆ溶液を加え、６
０℃に昇温後、先に得たグリニヤール試薬を滴下し滴下
後２時間熟成した。反応液を水冷希塩酸に注加し、ベン
ゼンで抽出した後、飽和食塩水で洗液が中性になるまで
洗浄し、芒硝で脱水した後、溶媒を留去し、残留物をヘ
キサンで処理し、ヘキサン不溶物をアセトンで再結晶し
て（Ｓ）−４−（４−メチルヘキシル）オキシ−４＃−
デシル−ｐ−ターフェニル ０．２ｇ（１１％）を得た
。b, p136~141'o/0.4 mmHg A synthesis reactor was charged with magnesium powder 0.359 and a small piece of iodine, and a small amount of the THF 10ml solution of 4g of 4-decylbromobenzene obtained in (b) above was added to it. The reaction was initiated by foaming. Next, the remaining THF solution was added dropwise while stirring to maintain reflux, and after the dropwise addition, the solution was refluxed and stirred for 2 hours to prepare a Grignard reagent. In another container, dichlorbistriphenylphosphine palladium A(C(2tP)
d(PPhs)z) 50IIg and THF3+m(+ were charged, 0.1mff of a 1M hexane solution of diisobutylaluminum hydride ((iso-CaHs)xAI2H) was added thereto, and then the (S) obtained in the above (a)
Add a solution of 1.4 g of -4-(4-methylhexyl)oxy-4'-brombiphenyl in 5 mff of THF, and
After raising the temperature to 0°C, the previously obtained Grignard reagent was added dropwise and the mixture was aged for 2 hours. The reaction solution was poured into water-cooled diluted hydrochloric acid, extracted with benzene, washed with saturated brine until the washings became neutral, dehydrated with Glauber's salt, the solvent was distilled off, and the residue was treated with hexane. , recrystallize the hexane insoluble material from acetone to obtain (S)-4-(4-methylhexyl)oxy-4#-
0.2 g (11%) of decyl-p-terphenyl was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４８４に分子イオンビークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
It was confirmed that a molecular ion peak was observed in 484 by R and Mass analysis, and that the obtained substance was the desired substance in view of the raw materials used.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 １７
実施例１６（Ｃ）において、４−デシルブロムベンゼン
４ｇに替えて実施例１ （ａ）で得られる４−ペンチ
ルブロムベンゼン３．０６９を用い、他ハ実施例１６と
同様に操作して（Ｓ）−４−（４−メチルヘキシル）オ
キシ−４“−ペンチル−ｐ−９−フェニル０．４１９
（２５％）を得た。Example 17 In Example 16 (C), 3.069 g of 4-pentylbromobenzene obtained in Example 1 (a) was used in place of 4 g of 4-decylbromobenzene, and the other cells were operated in the same manner as in Example 16. (S)-4-(4-methylhexyl)oxy-4"-pentyl-p-9-phenyl 0.419
(25%) was obtained.
この物の純度はＨＰＬＣで９８％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４１４に分子イオンビークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 98% or higher by HPLC. Also I
In view of the fact that a molecular ion peak was observed in 414 by R and Mass analysis, and the raw materials used, it was confirmed that the obtained substance was the desired product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 １８
反応器にｐ−ターフェニル ５．７ｇ及び塩化メチレン
４０ｍＱを仕込み、撹拌下に０℃で無水塩化アルミニ
ウム ４９を加え、次いでデカノイルクロライド５．２
ｇの塩化メチレン １０＋ｘｆｆ溶液を滴下し、滴下後
５時間撹拌した。反応液を希塩酸に注加し、充分に撹拌
した後、不溶物を濾取し、水洗し、乾燥して４−デカノ
イル−ｐ−ターフェニル６．８ｇ（７１％）を得た。Example 18 A reactor was charged with 5.7 g of p-terphenyl and 40 mQ of methylene chloride, and 49% of anhydrous aluminum chloride was added at 0°C with stirring, followed by 5.2% of decanoyl chloride.
A methylene chloride 10+xff solution of g was added dropwise, and the mixture was stirred for 5 hours after the dropwise addition. After pouring the reaction solution into diluted hydrochloric acid and stirring thoroughly, insoluble matter was collected by filtration, washed with water, and dried to obtain 6.8 g (71%) of 4-decanoyl-p-terphenyl.
ＨＰＬＣ９３，３％
反応器に上記（ａ）で得た４−デカノイル−ｐ−ターフ
ェニル ６．８９．ジエチレングリコール５Ｑ＋ｍｆｆ
、 ８０％抱水ヒドラジン３．４９及び、８８％苛性カ
リ １．８９の水 ４ｍ１２溶液を仕込み、撹拌下に１
３０°Ｃで５時間、次いで水を留去させながら昇温し、
２１０’Ｏで３時間反応（［料の消失をＴＬＣで確認）
した。反応液を希塩酸に注加し、ベンゼンで抽出し、水
洗し、芒硝で脱水した後、溶媒を留去し残留物をＴＨＦ
で再結晶して４−デシル−ｐ−ターフェニル５．１ｇ（
７７，６％）を得た。HPLC93.3% 4-decanoyl-p-terphenyl obtained in above (a) in a reactor 6.89. Diethylene glycol 5Q+mff
, A solution of 3.49 80% hydrazine hydrate and 1.89 ml of 88% caustic potassium hydrate in water was charged, and 12 mL of water was added under stirring.
5 hours at 30°C, then increase the temperature while distilling off water,
React at 210'O for 3 hours (confirm disappearance of material by TLC)
did. The reaction solution was poured into diluted hydrochloric acid, extracted with benzene, washed with water, and dehydrated with sodium sulfate.The solvent was distilled off and the residue was dissolved in THF.
Recrystallized with 5.1 g of 4-decyl-p-terphenyl (
77.6%).
ＨＰＬＣ９７，３％
（ｃ） Ｃ＋ｏＨｕ−〈＝〉ｉ〈＝〉−ぐつ−ＣＯＣ
Ｈｓ （７） 合成反応器に上記（ｂ）で得た４−デシ
ル−ｐ−ターフェニル ５ｇ及び塩化メチレン ３０ｍ
１２を仕込み、撹拌下に０℃で無水塩化アルミニウム２
．２９を加え、次いでアセチルクロライド１．３ｇの塩
化メチレン ｌ Ｏ＋ｍＱ溶液を滴下した。滴下後、原
料の消失するまで（ＴＬＣで確認）同温度で撹拌反応し
た。６時間を要した。反応液を氷／希塩酸に注加し、析
出物を濾取し、水洗した。この物と、濾液の塩化メチレ
ン層を水洗した後、芒硝で脱水し、溶媒を留去して得ら
れる残留物とを合わせ、ＴＨＦで再結晶して４−アセチ
ル−４＃−デシル−ｐ−ターフェニル４．４ｇ（７８％
）を得た。HPLC97.3% (c) C+oHu-〈=〉i〈=〉-gutsu-COC
Hs (7) 5 g of 4-decyl-p-terphenyl obtained in (b) above and 30 m of methylene chloride were placed in a synthesis reactor.
12 and anhydrous aluminum chloride 2 at 0℃ under stirring.
．． 29 was added thereto, and then a solution of 1.3 g of acetyl chloride in methylene chloride 1 O+mQ was added dropwise. After the dropwise addition, the reaction was stirred at the same temperature until the raw materials disappeared (as confirmed by TLC). It took 6 hours. The reaction solution was poured into ice/diluted hydrochloric acid, and the precipitate was collected by filtration and washed with water. This material was combined with the residue obtained by washing the methylene chloride layer of the filtrate with water, dehydrating it with sodium sulfate, and distilling off the solvent, and recrystallizing it with THF. Terphenyl 4.4g (78%
) was obtained.
ＨＰＬＣ９９，４％
（ｄ） ＣＩＩＩＨ！＋−〈７ ｚ ７ Ｓ ７
０Ｈの合成反応器に上記（Ｃ）で得た４−アセチル−４
＃デシル−ｐ−ターフェニル ２ｇ及び塩化メチレン２
０ｍｆｆを仕込み、室温撹拌下に、８８％ギ［８９、無
水酢酸 ３ｇ及び濃硫酸 ｌ攬Ｑを順次加え、更に３５
％過酸化水素水 ３ｇを１４°Ｃで滴下した。HPLC99.4% (d) CIIIH! +-〈7 z 7 S 7
4-acetyl-4 obtained in (C) above in the 0H synthesis reactor
#Decyl-p-terphenyl 2g and methylene chloride 2
0 mff was charged, and while stirring at room temperature, 88% ghee [89], 3 g of acetic anhydride, and concentrated sulfuric acid 1Q were sequentially added, and further 35%
% hydrogen peroxide solution was added dropwise at 14°C.
滴下後、ＴＬＣで原料が消失するまで適宜３５％過酸化
水素水を加えながら、４０℃で撹拌反応させた。反応液
を氷水に注加し、塩化メチレン層を分取し、芒硝で脱水
し、溶媒を留去して残留分（４−アセチルオキシ−４＃
−デシル−ｐ−ターフェニル）を４ｇ得た。この残留分
４ｇ、エタノール１５０ｍＱ及び８５％苛性カリ１９の
水２ｖａＱ溶液を反応器に仕込み、１３時間撹拌還流し
た。反応液を水に注加し、液性を塩酸酸性とした後、エ
ーテルで抽出し、水洗し、芒硝で脱水し、溶媒を留去後
、残留分をヘキサンで再結晶して４−ヒドロキシ−４“
−デシル−ｐ−ターフェニル１．２ｇ（６３％）を得た
。After the dropwise addition, the mixture was reacted with stirring at 40° C. while adding 35% hydrogen peroxide as needed until the raw materials disappeared by TLC. The reaction solution was poured into ice water, the methylene chloride layer was separated, dehydrated with sodium sulfate, the solvent was distilled off, and the residue (4-acetyloxy-4#
-decyl-p-terphenyl) was obtained. 4 g of this residue, 150 mQ of ethanol, and a 2 vaQ solution of 85% caustic potassium 19 in water were charged into a reactor, and the mixture was stirred and refluxed for 13 hours. The reaction solution was poured into water to make the solution acidic with hydrochloric acid, extracted with ether, washed with water, dehydrated with Glauber's salt, the solvent was distilled off, and the residue was recrystallized with hexane to obtain 4-hydroxy- 4“
1.2 g (63%) of -decyl-p-terphenyl was obtained.
合成
反応器に上記（ｄ）で得た４−ヒドロキシ−４“／７
２０ａＬ炭酸カリウム０．２９及び（Ｓ）−１−メチル
へキシルトシレート ０．３５９を仕込み、１７時間撹
拌還流した。反応液を吸引濾過して固形物を除き、濾液
を濃縮し、残留分をシリカゲルカラムクロマトグラフィ
ー（ヘキサン／ベンゼン−５／ｌ）で精製して（Ｒ）−
４−（１−メチルヘキシル）オキシ−４“−デシル−ｐ
−ターフェニル０．１３９ （２７％）を得を二。4-hydroxy-4"/7 obtained in the above (d) in the synthesis reactor
0.29 of 20aL potassium carbonate and 0.359 of (S)-1-methylhexyl tosylate were charged, and the mixture was stirred and refluxed for 17 hours. The reaction solution was suction-filtered to remove solids, the filtrate was concentrated, and the residue was purified by silica gel column chromatography (hexane/benzene-5/l) to obtain (R)-
4-(1-methylhexyl)oxy-4"-decyl-p
-terphenyl 0.139 (27%) was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４８４に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 484 in R and Mass analysis and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 １９ ＣＨ。Example 19 CH.
（ａ ） Ｃｔ Ｈａ ＣＨ（ＣＨり！ ＣＯＯＨの
合成本
反応器に過マンガン酸カリ １６９．水３００＋＊１２
及−デシルーｐ−ターフェニル ０．４９．２−ブタび
８５％苛性カリ ２ｇを仕込み、室温撹拌下に（Ｓ）−
４−メチルヘキサノール１０ｇを滴下し、滴下後４時間
撹拌反応させた。反応液を吸引濾過して固形物を除き、
濾液をエーテルで抽出し、水層を分取して塩酸酸性とし
た後、クロロホルムで抽出し、芒硝で脱水し、溶媒を留
去して残留分（（Ｓ）−４−メチルヘキサン酸） ６．
５９ （５９％）を得た。(a) Ct Ha CH (CHri! Synthesis of COOH) Potassium permanganate 169.Water 300+*12
and -decyl-p-terphenyl 0.49.2-Buta and 2 g of 85% caustic potassium were charged and (S)-
10 g of 4-methylhexanol was added dropwise, and the mixture was stirred and reacted for 4 hours. Suction filter the reaction solution to remove solids,
The filtrate was extracted with ether, the aqueous layer was separated, acidified with hydrochloric acid, extracted with chloroform, dehydrated with Glauber's salt, and the solvent was distilled off to obtain a residue ((S)-4-methylhexanoic acid). ．．
59 (59%).
ＧＬＣ９８，６％
成
反応器に実施例１８（ｄ）で得られる４−ヒドロキシ−
４“−デシル−ｐ−ターフェニル ０．５ｇ。4-Hydroxy- obtained in Example 18(d) was placed in a GLC98.6% reaction vessel.
4"-decyl-p-terphenyl 0.5 g.
脱水クロロホルム ２０ｍＬ ４−ジメチルアミノピリ
ジン０．１７９．ジシクロへキシルカルボジイミド（Ｄ
ＣＣ） ０．３９及び（ａ）で得た（Ｓ）−４−メチル
ヘキサン酸０．２ｇを加え、室温で１６時間撹拌反応さ
せた。反応液を濾過して固形物を除き、濾液を水洗し、
希塩酸で洗い、水洗した後、芒硝で脱水し、溶媒を留去
した残留分をシリカゲルカラムクロマトグラフィー（ヘ
キサン／ベンゼン−２／１−ｈｌ／１）で精製して（Ｓ
）−４−デシル−４”−（４−メチルヘキサノイル）オ
キシ−ｐ−ターフェニル０．４４９ （６９％）を得た
。Dehydrated chloroform 20mL 4-dimethylaminopyridine 0.179. Dicyclohexylcarbodiimide (D
CC) 0.39 and 0.2 g of (S)-4-methylhexanoic acid obtained in (a) were added, and the mixture was stirred and reacted at room temperature for 16 hours. Filter the reaction solution to remove solids, wash the filtrate with water,
After washing with dilute hydrochloric acid and water, it was dehydrated with Glauber's salt and the solvent was distilled off. The residue was purified by silica gel column chromatography (hexane/benzene-2/1-hl/1) to obtain (S
)-4-decyl-4"-(4-methylhexanoyl)oxy-p-terphenyl 0.449 (69%) was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４９８に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 498 in R and Mass analysis and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 ２０
反応器に実施例１８（ｃ）で得られる４−アセチル−４
＃−デシル−ｐ−ターフェニル １．０９並びに１．４
−ジオキサン４０ｔＱを仕込み、１６〜１８℃で撹拌下
に、臭素１２ｇと２０％苛性ソーダ水溶液６２２から調
製した次亜臭素酸ソーダ水溶液１２ｒＲａを滴下後、Ｔ
ＬＣで原料スポットが消失するまで適宜次亜臭素酸ソー
ダ水溶液を添加し、４０℃で撹拌反応した。反応液を希
塩酸に注加し、ベンゼンで抽出し、水洗し、芒硝で脱水
した後、溶媒を留去し、残留分（４−デシル−ｐ−ター
フェニル−４″−カルボン酸） ０．９９ （９０％）
を得た。Example 20 4-acetyl-4 obtained in Example 18(c) in a reactor
#-decyl-p-terphenyl 1.09 and 1.4
- Charge 40tQ of dioxane, dropwise add 12rRa of sodium hypobromite aqueous solution prepared from 12g of bromine and 20% aqueous solution of caustic soda 622 while stirring at 16-18°C, and then
An aqueous solution of sodium hypobromite was appropriately added until raw material spots disappeared by LC, and the mixture was stirred and reacted at 40°C. The reaction solution was poured into dilute hydrochloric acid, extracted with benzene, washed with water, and dehydrated with sodium sulfate.The solvent was distilled off, and the residue (4-decyl-p-terphenyl-4''-carboxylic acid) was 0.99. (90%)
I got it.
の合成
反応器に上記（ａ）で得た４−デシル−ｐ−ターフェニ
ル−４“−カルボン酸０．３ｇ並びに塩化チオニル４ｒ
ａＱを仕込み、５時間撹拌還流後、ベンゼンを加えて減
圧下に蒸留して過剰の塩化チオニル並びにベンゼンを留
去した。得られた残留分（４−デシル−ｐ−ターフェニ
ル−４＃−カルボン酸クロライド）、 （Ｓ）−４−メ
チルヘキサノール０．１６９．ピリ９フＱ、５ｍ１ｌ並
ヒにベンゼン１０ｍｆｆを別の反応器に仕込み、８時間
還流撹拌後、反応液を水に注加し、希アンモニア水を加
えて撹拌し、不溶物を除き、ベンゼン層を水洗し、芒硝
で脱水し、溶媒を留去して得られた残留分をシリカゲル
カラムクロマトグラフィー（溶出液ベンゼン／ヘキサン
−２／３）で精製しくＳ） −４−（（４−メチルヘキ
シル）オキシフカルボニル−４＃−デシル−ｐ−ターフ
ェニル０．１９（２７％）を得た。0.3 g of 4-decyl-p-terphenyl-4"-carboxylic acid obtained in (a) above and thionyl chloride 4r were added to a synthesis reactor.
aQ was charged, and after stirring and refluxing for 5 hours, benzene was added and distilled under reduced pressure to remove excess thionyl chloride and benzene. The resulting residue (4-decyl-p-terphenyl-4#-carboxylic acid chloride), (S)-4-methylhexanol 0.169. Pyri 9FQ, 5 ml and 10 mff of benzene were charged in another reactor, and after stirring under reflux for 8 hours, the reaction solution was poured into water, diluted aqueous ammonia was added and stirred, insoluble matter was removed, and the benzene layer The residue obtained by distilling off the solvent was purified by silica gel column chromatography (eluent: benzene/hexane-2/3). ) Oxyphcarbonyl-4#-decyl-p-terphenyl 0.19 (27%) was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で５１２に分子イオンビークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
It was confirmed that a molecular ion peak was observed in 512 by R and Mass analysis, and that the obtained substance was the desired substance in view of the raw materials used.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表１に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 1.
実施例 ２１
反応器に２−フルオロフェノール１５９、オクチルブロ
マイド２５．９ｇ、炭酸カリウム４６．２ｇ並びにシク
ロへキサノン １５０ｍ＋（２を仕込み、１２０〜１３
０℃で１２時間撹拌した。反応液を希塩酸に注加し、ベ
ンゼンで抽出し、水洗し、芒硝で乾燥した後溶媒を留去
した。残留分並びにクロロホルム１００１１１２を別の
反応器に仕込み、室温撹拌下、臭素４４ｇを滴下し、さ
らに同温度で６時間撹拌した後着苛性ソーダ水溶液に注
加し撹拌した。Example 21 A reactor was charged with 159 2-fluorophenol, 25.9 g of octyl bromide, 46.2 g of potassium carbonate, and 150 m+(2) of cyclohexanone.
Stirred at 0°C for 12 hours. The reaction solution was poured into diluted hydrochloric acid, extracted with benzene, washed with water, dried over sodium sulfate, and then the solvent was distilled off. The residue and chloroform 1001112 were charged into another reactor, and 44 g of bromine was added dropwise to the reactor while stirring at room temperature, and the mixture was further stirred at the same temperature for 6 hours, then poured into an aqueous solution of caustic soda and stirred.
クロロホルム層を水洗し、芒硝で脱水し、溶媒を留去し
た残留分を減圧蒸留して、４−オクチルオキシ−３−フ
ルオロブロムベンゼン ３２９（７８，８％）を得た。The chloroform layer was washed with water, dehydrated with Glauber's salt, the solvent was distilled off, and the residue was distilled under reduced pressure to obtain 4-octyloxy-3-fluorobromobenzene 329 (78.8%).
ｂ、ｐ１２２〜１３０℃／ ０．３ ｍ＋ａＨｇル２．
２９（７２％）を得た。b, p122-130℃/0.3 m+aHg 2.
29 (72%) were obtained.
この物の純度はＨＰＬＣで９８％以上であった。またＩ
Ｒ及びＭａｓｓ分析で５０４に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認゛した。The purity of this product was 98% or higher by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 504 in R and Mass analysis and the raw materials used, it was confirmed that the obtained substance was the desired product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表２に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 2.
実施例 ２２
実施例４（ｅ）における４−才クチルオキシブロムベン
ゼン３．４ｇに替えて上記（ａ）で得た４−オクチルオ
キシ−３−フルオロブロムベンゼン３．６ｇを用い、又
、（Ｓ）−４−（２−メチルブチル）オキシ−２′−フ
ルオロ−４′−ブロムビフェニル２．０ｇに替えて実施
例１２（ｃ）で得られる４−オクチルオキシ−４′−ブ
ロムビフェニル ２．１ｇを用い、他は実施例４と同様
に操作して４．４′−ジオクチルオキシ−３−フルオロ
−ｐ−ターフェニ実施例４（ｅ）における４−オクチル
オキシブロムベンゼン３．４ｇに替えて実施例２１（ａ
）で得られる４−オクチルオキシ−３−フルオロブロム
ベンゼン３．６ｇを用い、又、（Ｓ）−４−（２−メチ
ルブチル）オキシ−２′−フルオロ−４’−フロムビフ
ェニル ２．０ｇに替えて、４−へブチル−４′−ブロ
ムビフェニル ２．０ｇを用い、他は実施例４と同様に
操作して４−オクチルオキシ−３−フルオロ−４＃−へ
ブチル−ｐ−ターフェニル０．４８ｇ（１７％）を得た
。Example 22 3.4 g of 4-octyloxybromobenzene in Example 4(e) was replaced with 3.6 g of 4-octyloxy-3-fluorobromobenzene obtained in (a) above, and (S )-4-(2-Methylbutyl)oxy-2'-fluoro-4'-brombiphenyl (2.0 g) was replaced with 2.1 g of 4-octyloxy-4'-brombiphenyl obtained in Example 12(c). 4.4'-dioctyloxy-3-fluoro-p-terphene was used in Example 21 in place of 3.4 g of 4-octyloxybromobenzene in Example 4(e). (a
) using 3.6 g of 4-octyloxy-3-fluorobromobenzene obtained in ), and replacing it with 2.0 g of (S)-4-(2-methylbutyl)oxy-2'-fluoro-4'-frombiphenyl. 4-octyloxy-3-fluoro-4#-hebutyl-p-terphenyl was prepared in the same manner as in Example 4 except for using 2.0 g of 4-hebutyl-4'-brombiphenyl. 48g (17%) was obtained.
この物の純度はＨＰＬＣで９９％以上であった。またＩ
Ｒ及びＭａｓｓ分析で４７４に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 474 in R and Mass analysis, and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表２に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 2.
実施例 ２３
３．３′−ジフルオロ−ｐ−ターフェニル ０．４２９
（１３，９％）を得た。Example 23 3.3'-difluoro-p-terphenyl 0.429
(13.9%) was obtained.
この物の純度はＨＰＬＣで９８％以上であった。またＩ
Ｒ及びＭａｓｓ分析で５２２に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 98% or higher by HPLC. Also I
In view of the fact that a molecular ion peak was observed at 522 in R and Mass analysis, and the raw materials used, it was confirmed that the obtained substance was the target product.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表２に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 2.
実施例 ２４
実施例４（ｅ）における４−オクチルオキシブロムベン
ゼン３．４ｇに替えて実施例２１（ａ）で得られる４−
オクチルオキシ−３−フルオロブロムベンゼン３．６ｇ
を用い、又（Ｓ）−４−（２−メチルブチル）オキシ−
２′−フルオロ−４′−ブロムビフェニル２．０ｇに替
えて、実施例１５（ａ）で得られる４−オクチルオキシ
−２′−フルオロ−４′−ブロムビフェニル ２．２ｇ
を用い、他は実施例４と同様に操作して４，４＃−ジオ
クチルオキシ−実施例４（ｅ）における４−オクチルオ
キシブロムベンゼン３．４ｇに替えて実施例２１（ａ）
で得られる４−オクチルオキシ−３−フルオロブロムベ
ンゼン３．６ｇを用い、又、（Ｓ）−４−（２−メチル
ブチル）オキシ−２′−フルオロ−４′−ブロムビフェ
ニル２．０９に替えて、実施例６（ｂ）で得られる４−
オクチル−２′−フルオロ−４′−ブロムビフェニル
２．２ｇを用い、他は実施例４と同様に操作して４−オ
クチルオキシ−３，３′−ジフルオロ−４“−オクチル
−ｐ−ターフェニル１．０９（３２，６％）を得た。Example 24 In place of 3.4 g of 4-octyloxybromobenzene in Example 4(e), 4-obtained in Example 21(a) was used.
Octyloxy-3-fluorobrombenzene 3.6g
and (S)-4-(2-methylbutyl)oxy-
Instead of 2.0 g of 2'-fluoro-4'-brombiphenyl, 2.2 g of 4-octyloxy-2'-fluoro-4'-brombiphenyl obtained in Example 15(a) was used.
4,4#-dioctyloxy-Example 21(a) was used in place of 3.4 g of 4-octyloxybromobenzene in Example 4(e).
Using 3.6 g of 4-octyloxy-3-fluorobrombenzene obtained in , and replacing 2.09 g of (S)-4-(2-methylbutyl)oxy-2'-fluoro-4'-brombiphenyl. , 4- obtained in Example 6(b)
Octyl-2'-fluoro-4'-brombiphenyl
Using 2.2 g, the other procedures were the same as in Example 4 to obtain 1.09 (32.6%) of 4-octyloxy-3,3'-difluoro-4"-octyl-p-terphenyl. .
この物の純度はＨＰＬＣで９９％以上であった。また！
Ｒ及びＭａｓｓ分析で５０６に分子イオンピークが認め
られたこと、並びに用いた原料からみて、得られた物質
が目的物であることを確認した。The purity of this product was 99% or more by HPLC. Also!
It was confirmed that a molecular ion peak was observed at 506 in R and Mass analysis, and that the obtained substance was the target substance, considering the raw materials used.
この物をメトラーホットステージＦＰ−８２にはさみ、
偏光顕微鏡下で相変化を観察した。その結果を表２に示
す。Place this item on the Mettler Hot Stage FP-82,
Phase changes were observed under a polarizing microscope. The results are shown in Table 2.
時間を測定したところ１８０μｓθＣ（測定温度１００
℃。When the time was measured, it was 180 μs θC (measured temperature 100
℃.
印加電圧±２５Ｖ 、 ２００Ｈｚ）であった。The applied voltage was ±25 V, 200 Hz).
実施例２７
非カイラル物質でＳｍＣ相を有する、実施例２４で得ら
れた化合物とカイラル物質である、実施例１５で得られ
た化合物を、重量比９０：１０の割合で混合して液晶組
成物を作製した。この組成物は５６〜１０４℃でＳｍＣ
本相亀甲し、又、この組成物を用いて実施例２５と同様
にして、液晶素子を作製し、応答時間を測定したところ
３００μ５ｅｃ（測定温度１００℃、印加電圧±２５Ｖ
、 ２００Ｈｚ）であった。Example 27 A liquid crystal composition was prepared by mixing the compound obtained in Example 24, which is a non-chiral substance and has an SmC phase, and the compound obtained in Example 15, which is a chiral substance, at a weight ratio of 90:10. was created. This composition is SmC at 56-104℃.
Using this composition, a liquid crystal element was prepared in the same manner as in Example 25, and the response time was measured to be 300μ5ec (measurement temperature 100°C, applied voltage ±25V).
, 200Hz).
Claims (1)
の直鎖状又は分岐鎖状のアルキル基を示し、Ｙ及びＺは
、それぞれ、単結合、Ｏ、ＣＯＯ又はＯＣＯを示し、Ｘ
＿１、Ｘ＿２及びＸ＿３は、それぞれ、水素原子、フッ
素原子又は塩素原子を示す）で表されるｐ−ターフェニ
ル誘導体。 ２）一般式（ I ）におけるＸ＿１、Ｘ＿２及びＸ＿３
の中のいずれか２つがフッ素原子であり、他が水素原子
である請求項１記載のｐ−ターフェニル誘導体。 ３）一般式（ I ）におけるＸ＿１、Ｘ＿２及びＸ＿３
の中のいずれか２つが塩素原子であり、他が水素原子で
ある請求項１記載のｐ−ターフェニル誘導体。 ４）一般式（ I ）におけるＸ＿１、Ｘ＿２及びＸ＿３
の中のいずれか１つがフッ素原子であり、他が水素原子
である請求項１記載のｐ−ターフェニル誘導体。 ５）一般式（ I ）におけるＸ＿１、Ｘ＿２及びＸ＿３
の中のいずれか１つが塩素原子であり、他が水素原子で
ある請求項１記載のｐ−ターフェニル誘導体。 ６）一般式（ I ）におけるＸ＿１、Ｘ＿２及びＸ＿３
の中のＸ＿２がフッ素原子、又は塩素原子であり、他が
水素原子である請求項１記載のｐ−ターフェニル誘導体
。 ７）一般式 ▲数式、化学式、表等があります▼（ I ） （Ｒ＾１およびＲ＾２は、それぞれ炭素原子数１〜１８
の直鎖状又は分岐鎖状のアルキル基を示し、Ｙ及びＺは
、それぞれ、単結合、Ｏ、ＣＯＯ又はＯＣＯを示し、Ｘ
＿１、Ｘ＿２及びＸ＿３は、それぞれ、水素原子、フッ
素原子又は塩素原子を示す）で表されるｐ−ターフェニ
ル誘導体を少なくとも１種含有することを特徴とする液
晶組成物。 ８）一般式（ I ）におけるＸ＿１、Ｘ＿２及びＸ＿３
の中のいずれか２つがフッ素原子であり、他が水素原子
である請求項７記載の液晶組成物。 ９）一般式（ I ）におけるＸ＿１、Ｘ＿２及びＸ＿３
の中のいずれか２つが塩素原子であり、他が水素原子で
ある請求項７記載の液晶組成物。 １０）一般式（ I ）におけるＸ＿１、Ｘ＿２及びＸ＿
３の中のいずれか１つがフッ素原子であり、他が水素原
子である請求項７記載の液晶組成物。 １１）一般式（ I ）におけるＸ＿１、Ｘ＿２及びＸ＿
３の中のいずれか１つが塩素原子であり、他が水素原子
である請求項７記載の液晶組成物。 １２）一般式（ I ）におけるＸ＿１、Ｘ＿２及びＸ＿
３の中のＸ＿２がフッ素原子、又は塩素原子であり、他
が水素原子である請求項７記載の液晶組成物。[Claims] 1) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (I) (R^1 and R^2 each have a carbon atom number of 1 to 18
represents a linear or branched alkyl group, Y and Z each represent a single bond, O, COO or OCO, and X
_1, X_2 and X_3 each represent a hydrogen atom, a fluorine atom or a chlorine atom). 2) X_1, X_2 and X_3 in general formula (I)
The p-terphenyl derivative according to claim 1, wherein any two of these atoms are fluorine atoms and the others are hydrogen atoms. 3) X_1, X_2 and X_3 in general formula (I)
The p-terphenyl derivative according to claim 1, wherein any two of these atoms are chlorine atoms and the others are hydrogen atoms. 4) X_1, X_2 and X_3 in general formula (I)
The p-terphenyl derivative according to claim 1, wherein any one of them is a fluorine atom and the others are hydrogen atoms. 5) X_1, X_2 and X_3 in general formula (I)
The p-terphenyl derivative according to claim 1, wherein one of them is a chlorine atom and the other is a hydrogen atom. 6) X_1, X_2 and X_3 in general formula (I)
The p-terphenyl derivative according to claim 1, wherein X_2 in these is a fluorine atom or a chlorine atom, and the others are hydrogen atoms. 7) General formula▲Mathematical formula, chemical formula, table, etc.▼(I) (R^1 and R^2 each have a carbon atom number of 1 to 18
represents a linear or branched alkyl group, Y and Z each represent a single bond, O, COO or OCO, and X
_1, X_2, and X_3 each represent a hydrogen atom, a fluorine atom, or a chlorine atom) A liquid crystal composition containing at least one p-terphenyl derivative. 8) X_1, X_2 and X_3 in general formula (I)
8. The liquid crystal composition according to claim 7, wherein any two of these atoms are fluorine atoms and the others are hydrogen atoms. 9) X_1, X_2 and X_3 in general formula (I)
8. The liquid crystal composition according to claim 7, wherein any two of these atoms are chlorine atoms and the others are hydrogen atoms. 10) X_1, X_2 and X_ in general formula (I)
8. The liquid crystal composition according to claim 7, wherein any one of 3 is a fluorine atom and the others are hydrogen atoms. 11) X_1, X_2 and X_ in general formula (I)
8. The liquid crystal composition according to claim 7, wherein any one of 3 is a chlorine atom and the others are hydrogen atoms. 12) X_1, X_2 and X_ in general formula (I)
8. The liquid crystal composition according to claim 7, wherein X_2 in 3 is a fluorine atom or a chlorine atom, and the others are hydrogen atoms.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63216294A JP2655333B2 (en) | 1988-09-01 | 1988-09-01 | Novel p-terphenyl derivative and liquid crystal composition |
| DE68919312T DE68919312T2 (en) | 1988-09-01 | 1989-08-29 | p-terphenyl derivatives and liquid crystal compositions. |
| EP89115920A EP0360042B1 (en) | 1988-09-01 | 1989-08-29 | p-Terphenyl derivatives and liquid crystalline compositions |
| EP89115921A EP0360043B1 (en) | 1988-09-01 | 1989-08-29 | p-Terphenyl derivatives and liquid crystalline compositions |
| DE89115920T DE68910453T2 (en) | 1988-09-01 | 1989-08-29 | p-terphenyl derivatives and liquid crystal compositions. |
| US07/892,735 US5382380A (en) | 1988-09-01 | 1992-06-01 | P-terphenyl derivatives and liquid crystalline compositions |
| US08/157,339 US5494605A (en) | 1988-09-01 | 1993-11-24 | P-terphenyl derivatives and liquid crystalline compositions |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63216294A JP2655333B2 (en) | 1988-09-01 | 1988-09-01 | Novel p-terphenyl derivative and liquid crystal composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0267232A true JPH0267232A (en) | 1990-03-07 |
| JP2655333B2 JP2655333B2 (en) | 1997-09-17 |
Family
ID=16686283
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63216294A Expired - Lifetime JP2655333B2 (en) | 1988-09-01 | 1988-09-01 | Novel p-terphenyl derivative and liquid crystal composition |
Country Status (4)
| Country | Link |
|---|---|
| US (2) | US5382380A (en) |
| EP (2) | EP0360042B1 (en) |
| JP (1) | JP2655333B2 (en) |
| DE (2) | DE68919312T2 (en) |
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|---|---|---|---|---|
| WO1998013323A1 (en) * | 1996-09-25 | 1998-04-02 | Chisso Corporation | Substituted benzene derivative, liquid-crystal composition, and liquid-crystal display element |
| WO1998023562A1 (en) * | 1996-11-25 | 1998-06-04 | Chisso Corporation | 3,3'-difluorobiphenyl derivatives, liquid crystal compositions, and liquid crystal display elements |
| US6579577B2 (en) | 1996-09-25 | 2003-06-17 | Chisso Corporation | Substituted benzene derivative, liquid crystal composition, and liquid crystal display element |
| JP2011016986A (en) * | 2009-06-08 | 2011-01-27 | Chisso Corp | Liquid crystal composition and liquid crystal-displaying element |
| WO2011040171A1 (en) | 2009-09-30 | 2011-04-07 | チッソ株式会社 | Liquid crystal composition and liquid crystal display element |
| JP2011084730A (en) * | 2009-09-15 | 2011-04-28 | Chisso Corp | Liquid crystal composition and liquid crystal display device |
| KR20120003861A (en) | 2009-03-16 | 2012-01-11 | 제이엔씨 주식회사 | Liquid-crystal composition and liquid-crystal display element |
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|---|---|---|---|---|
| JP2575885B2 (en) * | 1989-08-23 | 1997-01-29 | シャープ株式会社 | Liquid crystal composition and liquid crystal device containing the same |
| US5271867A (en) * | 1989-08-23 | 1993-12-21 | Sharp Kabushiki Kaisha | Liquid crystal composition and liquid crystal device containing the same |
| DE4236104A1 (en) * | 1992-10-26 | 1994-04-28 | Hoechst Ag | Bifunctional primary products for the production of liquid crystals |
| US5417885A (en) * | 1993-08-03 | 1995-05-23 | Showa Shell Sekiyu Kabushiki Kaisha | Antiferroelectric liquid crystal compound |
| GB2285810A (en) * | 1994-01-10 | 1995-07-26 | Secr Defence | Smectic liquid crystal materials for electroclinic or nonlinear optic devices |
| GB9411233D0 (en) * | 1994-06-04 | 1994-07-27 | Central Research Lab Ltd | Liquid crystal compositions |
| GB2296253B (en) * | 1994-12-22 | 1998-11-25 | Merck Patent Gmbh | Nematic liquid crystal mixtures |
| DE19645248A1 (en) * | 1995-11-17 | 1997-05-22 | Merck Patent Gmbh | New benzene derivatives having chiral terminal groups |
| EP0933346B1 (en) * | 1996-07-31 | 2003-12-10 | Shionogi & Co., Ltd. | NOVEL p-TERPHENYL COMPOUNDS |
| WO1998011173A1 (en) * | 1996-09-12 | 1998-03-19 | Samsung Display Devices Co., Ltd. | Liquid crystal materials |
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| EP1141172A1 (en) * | 1998-11-17 | 2001-10-10 | QinetiQ Limited | Liquid crystal materials |
| GB2362882A (en) * | 2000-06-02 | 2001-12-05 | Sharp Kk | Liquid crystalline optionally laterally fluorinated terphenyl with chiral 3,4-di[(un)saturated-alkoxy]butoxy or 1,4-di[(un)saturated-alkoxy]but-2-oxy terminus |
| GB0122190D0 (en) * | 2001-09-14 | 2001-10-31 | Qinetiq Ltd | Novel compounds |
| CN100560553C (en) * | 2007-01-19 | 2009-11-18 | 烟台九目化学制品有限公司 | The preparation method of phenol analog derivative |
| CN102186945B (en) * | 2008-09-17 | 2014-06-25 | 特拉根Lc化学股份公司 | Chiral compounds, cholesteric and ferroelectric liquid crystal compositions comprising these chiral compounds, and liquid crystal displays comprising these liquid crystal compositions |
| PL217692B1 (en) * | 2011-07-20 | 2014-08-29 | Wojskowa Akad Tech | Nematic compounds and nematic media containing them with a positive or negative dielectric anisotropy |
| CN110229676A (en) * | 2019-06-12 | 2019-09-13 | 晶美晟光电材料（南京）有限公司 | A kind of liquid-crystal composition of negative permittivity and its application |
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| JPS6051135A (en) * | 1983-07-22 | 1985-03-22 | イギリス国 | Compound containing fluorobiphenyl-yl group and use for liquid crystal material and device production |
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| EP0084194B1 (en) * | 1982-01-14 | 1986-04-30 | MERCK PATENT GmbH | Liquid crystal mixtures |
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| US4654162A (en) * | 1984-08-13 | 1987-03-31 | Chisso Corporation | Alcohol derivatives |
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| DE3587601T2 (en) * | 1984-10-18 | 1994-03-10 | Chisso Corp | Ferroelectric chiral smectic liquid crystal composition. |
| US4780240A (en) * | 1985-08-02 | 1988-10-25 | Chisso Corporation | Liquid crystal composition |
| GB8520715D0 (en) * | 1985-08-19 | 1985-09-25 | Secr Defence | Secondary alcohol derivatives |
| EP0260275A1 (en) * | 1986-02-17 | 1988-03-23 | MERCK PATENT GmbH | Optically active compounds |
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| JP2538578B2 (en) * | 1987-02-02 | 1996-09-25 | チッソ株式会社 | 2-Substituted alkyl ethers and liquid crystal composition |
| JP2594266B2 (en) * | 1987-02-05 | 1997-03-26 | チッソ株式会社 | Optically active 2-alkoxy-propyl ethers and liquid crystal composition |
| GB8703103D0 (en) * | 1987-02-11 | 1987-03-18 | Secr Defence | Terphenyl derivatives |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1998013323A1 (en) * | 1996-09-25 | 1998-04-02 | Chisso Corporation | Substituted benzene derivative, liquid-crystal composition, and liquid-crystal display element |
| US6579577B2 (en) | 1996-09-25 | 2003-06-17 | Chisso Corporation | Substituted benzene derivative, liquid crystal composition, and liquid crystal display element |
| WO1998023562A1 (en) * | 1996-11-25 | 1998-06-04 | Chisso Corporation | 3,3'-difluorobiphenyl derivatives, liquid crystal compositions, and liquid crystal display elements |
| US6197217B1 (en) | 1996-11-25 | 2001-03-06 | Chisso Corporation | 3,3′-difluorobiphenyl derivatives, liquid crystal compositions, and liquid crystal display elements |
| KR20120003861A (en) | 2009-03-16 | 2012-01-11 | 제이엔씨 주식회사 | Liquid-crystal composition and liquid-crystal display element |
| US8609207B2 (en) | 2009-03-16 | 2013-12-17 | Jnc Corporation | Liquid crystal composition and liquid crystal display device |
| US8071182B2 (en) | 2009-06-08 | 2011-12-06 | Jnc Corporation | Liquid crystal composition and liquid crystal display device |
| JP2011016986A (en) * | 2009-06-08 | 2011-01-27 | Chisso Corp | Liquid crystal composition and liquid crystal-displaying element |
| JP2011084730A (en) * | 2009-09-15 | 2011-04-28 | Chisso Corp | Liquid crystal composition and liquid crystal display device |
| US8057867B2 (en) | 2009-09-15 | 2011-11-15 | Jnc Corporation | Liquid crystal composition and liquid crystal display device |
| WO2011040171A1 (en) | 2009-09-30 | 2011-04-07 | チッソ株式会社 | Liquid crystal composition and liquid crystal display element |
| KR20120099390A (en) | 2009-09-30 | 2012-09-10 | 제이엔씨 석유 화학 주식회사 | Liquid crystal composition and liquid crystal display element |
| US8586152B2 (en) | 2009-09-30 | 2013-11-19 | Jnc Corporation | Liquid crystal composition and liquid crystal display device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2655333B2 (en) | 1997-09-17 |
| EP0360042A1 (en) | 1990-03-28 |
| US5494605A (en) | 1996-02-27 |
| DE68910453T2 (en) | 1994-04-14 |
| EP0360043A1 (en) | 1990-03-28 |
| DE68910453D1 (en) | 1993-12-09 |
| DE68919312D1 (en) | 1994-12-15 |
| EP0360042B1 (en) | 1993-11-03 |
| US5382380A (en) | 1995-01-17 |
| DE68919312T2 (en) | 1995-03-23 |
| EP0360043B1 (en) | 1994-11-09 |
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